Resin composition and resin molded body thereof
The present invention aims to obtain a resin composition with low thermal expansion property by suppressing functional deterioration in negative thermal expansion property when a negative thermal expansion material is added to a thermoplastic resin and heat-processed. The present invention provides a resin composition including metal oxide particles and a thermoplastic resin, both having a negative thermal expansion property. The negative thermal expansion of the particles is attributed to a crystal phase transition, which is driven by electron transfer between the constituent metals, and a covalent protective layer that inhibits the electron transfer is formed between the particles and the thermoplastic resin.
1 . A resin composition comprising:
metal oxide particles with a negative coefficient of linear expansion at 0° C. to 60° C.; and
a thermoplastic resin with a positive coefficient of linear expansion at 0° C. to 60° C.,
wherein:
the metal oxide particles change in metal element valence during crystal phase transition;
a surface of the metal oxide particles is provided with a compound containing at least one metal element selected from the group consisting of Si, Al, and Ti;
the compound containing the metal element is a condensate of an alkoxide compound represented by formula (1) or (2):
SiR1 n1 R2 m1 (1)
wherein:
R1 is a functional group selected from the group consisting of a methyl group, a methoxy group, and an ethoxy group;
R2 is a functional group having 8 or less carbon atoms and having an end portion selected from the group consisting of any one of epoxy, amine, imine, and (meth)acryloxy groups;
n1 is a positive integer;
m1 is a positive integer or 0; and
n1+m1 is 4;
M 4 R3 n2 R4 m2 (2),
wherein:
M 4 is Al or Ti;
R3 is a functional group selected from the group consisting of an alkyl group having 8 or less carbon atoms and an alkoxy group having 8 or less carbon atoms;
R4 is a functional group having 8 or less carbon atoms and having an end portion selected from the group consisting of any one of epoxy, amine, imine, and (meth)acryloxy groups, phosphoric acid ester, and sulfonic acid ester;
when M 4 is Al, n2 is a positive integer, m2 is a positive integer or 0, and n2+m2 is 3; and
when M4 is Ti, n2 is a positive integer, m2 is a positive integer or 0, and n2+m2 is 4; and
the metal oxide particles are particles of a metal oxide represented by formula (A) or (B):
(Bi 1-x1 M 1 x1 )(Ni 1-x2 M 2 x2 )O y (A),
wherein:
M 1 is at least one metal element selected from the group consisting of lanthanoids, Y, and In;
M 2 is at least one metal element selected from the group consisting of Al, V, Cr, Mn, Fe, Co, Ga, and Sb;
x1, x2, and y are such that x1 is 0.02 to 0.15, x2 is 0.02 to 0.50, and y is 3 or less;
BiNi 1-x M 3 x O y (B),
wherein:
M 3 is at least one metal element selected from the group consisting of Al, V, Cr, Mn, Fe, Co, Ga, and Sb;
x is 0.02 to 0.50; and
y is 3 or less.
2 . The resin composition according to claim 1 , wherein a volume fraction of the metal oxide particles in the resin composition is 23% by volume to 33% by volume.
3 . The resin composition according to claim 1 , wherein the thermoplastic resin is at least one selected from the group consisting of a polycarbonate resin and a cycloolefin resin.
4 . A resin molded body comprising:
metal oxide particles with a negative coefficient of linear expansion at 0° C. to 60° C.; and
a resin with a positive coefficient of linear expansion at 0° C. to 60° C.,
wherein:
the metal oxide particles change in metal element valence during crystal phase transition;
a surface of the metal oxide particles is provided with a compound containing at least one metal element selected from the group consisting of Si, Al, and Ti;
the compound containing the metal element is a condensate of an alkoxide compound represented by formula (1) or (2):
SiR1 n1 R2 m1 (1)
wherein:
R1 is a functional group selected from the group consisting of a methyl group, a methoxy group, and an ethoxy group;
R2 is a functional group having 8 or less carbon atoms and having an end portion selected from the group consisting of any one of epoxy, amine, imine, and (meth)acryloxy groups;
n1 is a positive integer;
m1 is a positive integer or 0; and
n1+m1 is 4;
M 4 R3 n2 R4 m2 (2),
wherein:
M 4 is Al or Ti;
R3 is a functional group selected from the group consisting of an alkyl group having 8 or less carbon atoms and an alkoxy group having 8 or less carbon atoms;
R4 is a functional group having 8 or less carbon atoms and having an end portion selected from the group consisting of any one of epoxy, amine, imine, and (meth)acryloxy groups, phosphoric acid ester, and sulfonic acid ester;
when M 4 is Al, n2 is a positive integer, m2 is a positive integer or 0, and n2+m2 is 3; and
when M 4 is Ti, n2 is a positive integer, m2 is a positive integer or 0, and n2+m2 is 4; and
the metal oxide particles are particles of a metal oxide represented by formula (A) or (B):
(Bi 1-x1 M 1 x1 )(Ni 1-x2 M 2 x2 )O y (A),
wherein:
M 1 is at least one metal element selected from the group consisting of lanthanoids, Y, and In;
M 2 is at least one metal element selected from the group consisting of Al, V Cr, Mn, Fe, Co, Ga, and Sb;
x1, x2, and y are such that x1 is 0.02 to 0.15, x2 is 0.02 to 0.50, and y is 3 or less;
BiNi 1-x M 3 x O y (B),
wherein:
M 3 is at least one metal element selected from the group consisting of Al, V, Cr, Mn, Fe, Co, Ga, and Sb;
x is 0.02 to 0.50; and
y is 3 or less.
5 . The resin molded body according to claim 4 , wherein a coefficient of linear expansion of the resin molded body at 0° C. to 60° C. is greater than 0 ppm/° C. to 45 ppm/° C.
6 . A method of producing a resin molded body which includes metal oxide particles with a negative coefficient of linear expansion at 0° C. to 60° C. and a resin with a positive coefficient of linear expansion at 0° C. to 60° C., wherein the metal oxide particles change in metal element valence during crystal phase transition, the method comprising:
providing a compound containing at least one metal element selected from the group consisting of Si, Al, and Ti on a surface of the metal oxide particles;
mixing the metal oxide particles provided with the compound with the resin; and
molding the resin mixed with the metal oxide particles provided with the compound at a temperature of 100° C. to 300° C.,
wherein the compound containing the metal element is a condensate of an alkoxide compound represented by formula (1) or (2):
SiR1 n1 R2 m1 (1),
wherein:
R1 is a functional group selected from the group consisting of a methyl group, a methoxy group, and an ethoxy group;
R2 is a functional group having 8 or less carbon atoms and having an end portion selected from the group consisting of any one of epoxy, amine, imine, and (meth)acryloxy groups;
n1 is a positive integer;
m1 is a positive integer or 0; and
n1+m1 is 4;
M 4 R3 n2 R4 m2 (2),
wherein:
M 4 is Al or Ti;
R3 is a functional group selected from the group consisting of an alkyl group having 8 or less carbon atoms and an alkoxy group having 8 or less carbon atoms;
R4 is a functional group having 8 or less carbon atoms and having an end portion selected from the group consisting of any one of epoxy, amine, imine, and (meth)acryloxy groups, phosphoric acid ester, and sulfonic acid ester;
when M 4 is Al, n2 is a positive integer, m2 is a positive integer or 0, and n2+m2 is 3; and
when M 4 is Ti, n2 is a positive integer, m2 is a positive integer or 0, and n2+m2 is 4, and
wherein the metal oxide particles are particles of a metal oxide represented by formula (A) or (B):
(Bi 1-x1 M 1 x1 )(Ni 1-x2 M 2 x2 )O y (A),
wherein:
M 1 is at least one metal element selected from the group consisting of lanthanoids, Y, and In;
M 2 is at least one metal element selected from the group consisting of Al, V, Cr, Mn, Fe, Co, Ga, and Sb;
x1, x2, and y are such that x1 is 0.02 to 0.15, x2 is 0.02 to 0.50, and y is 3 or less;
BiNi 1-x M 3 x O y (B),
wherein:
M 3 is at least one metal element selected from the group consisting of Al, V, Cr, Mn, Fe, Co, Ga, and Sb;
x is 0.02 to 0.50; and
y is 3 or less.
7 . A lens barrel comprising:
a housing; and
an optical system including a plurality of lenses arranged within the housing,
wherein the housing is made of the resin molded body according to claim 4 .
8 . A catoptric element comprising:
a base material; and
a reflective film provided on the base material,
wherein the base material is made of the resin molded body according to claim 4 .
9 . The resin composition according to claim 1 , wherein the thermoplastic resin includes cycloolefin resin.
10 . A resin molded body produced by the method according to claim 6 .
11 . A lens barrel comprising:
a housing; and
an optical system including a plurality of lenses arranged within the housing,
wherein the housing is made of the resin molded body according to claim 10 .
12 . A catoptric element comprising:
a base material; and
a reflective film provided on the base material,
wherein the base material is made of the resin molded body according to claim 10 .
13 . A resin composition comprising:
metal oxide particles having a negative coefficient of linear expansion at 0° C. to 60° C. and represented by formula (B): BiNi 1-x Fe x O 3 (B), where x is 0.02 to 0.50; and
a thermoplastic resin with a positive coefficient of linear expansion at 0° C. to 60° C.,
wherein the metal oxide particles change in metal element valence during crystal phase transition, and a surface of the metal oxide particles is provided with a protective layer containing Si,
wherein the protective layer is a condensate of an alkoxide compound having one functional group selected from the group consisting of an epoxy functional group, an amino functional group, and a methacryl functional group, the alkoxide compound reacting under neutral conditions, and
wherein a converted value of a coefficient of linear expansion of the metal oxide particles in the thermoplastic resin is −178 ppm/° C. to −42 ppm/° C.
14 . A resin molded body comprising:
a molded body having the resin composition according to claim 13 ,
wherein a coefficient of linear expansion of the resin molded body at 0° C. to 60° C. is greater than 0 ppm/° C. and 45 ppm/° C. or less.
15 . A device comprising:
a member; and
the resin composition according to claim 13 configured to be arranged with the member,
wherein thermal expansion of the member is suppressed.
16 . A device comprising:
a member; and
the resin molded body according to claim 14 configured to be arranged with the member,
wherein thermal expansion of the member is suppressed.