CN109280309A - Solidification compound, formed body and its manufacturing method - Google Patents

Solidification compound, formed body and its manufacturing method Download PDF

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Publication number
CN109280309A
CN109280309A CN201810802148.5A CN201810802148A CN109280309A CN 109280309 A CN109280309 A CN 109280309A CN 201810802148 A CN201810802148 A CN 201810802148A CN 109280309 A CN109280309 A CN 109280309A
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China
Prior art keywords
ingredient
mass parts
solidification compound
methyl
range
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CN201810802148.5A
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Chinese (zh)
Inventor
新藤诚
隅田将
隅田将一
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority claimed from JP2018136015A external-priority patent/JP2019023287A/en
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of CN109280309A publication Critical patent/CN109280309A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Abstract

The present invention provides the solidification compound that can assemble well.The solidification compound contains ingredient below: the monomer of (A) containing 1 or more carbon-to-carbon unsaturated bond, (B) carbon black and (C) curing agent, relative to 100 mass parts of ingredient (A), the ingredient (B) is contained with 5 mass parts~45 mass parts range.

Description

Solidification compound, formed body and its manufacturing method
Technical field
The present invention relates to the manufacturing methods of solidification compound, formed body and formed body.
Background technique
Artificial marble has been used in the building materials of house etc. or kitchen utensils etc..For example, being described in patent document 1 Use the carbon particle of partial size 0.05mm or more.It is described in the embodiment 14 of patent document 1 by 7.6 weight of methacrylic resin Part, 30.4 parts by weight of methyl methacrylate, 2 parts by weight of trimethylol-propane trimethacrylate, 60 weight of aluminium hydroxide 2 parts by weight of active carbon, 0.02 weight of stearic acid of part, 297 μ pass of JIS standard mesh screen, 250 μ on and the apparent specific gravity 1.2 of particle Part and 2 is measured, 2- azo bis- (4- methoxyl group -2,4- methyl pentane nitriles) 0.02 parts by weight are obtained by mixing slurry, then, into Row heating, forms the artificial marble with grivelle.Described in patent document 2 can be used in building, automobile it is interior The SMC (sheet molding compound, sheet molding compound) for filling component uses resin combination (solidification compound).It records Acrylic resin containing cross-linking type, inorganic filling material, foaming agent, carbon black in the SMC resin combination of patent document 2 Equal pigment, release agent.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2-36266 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2004-175892 bulletin
Summary of the invention
In order to use BMC (bulk molding compound, tubular molding compound) it is expected with solidification compound Formed body, it is desirable that the surface of the solidification compound used to form the formed body is not easy to do, combine in the curability The surface of object, which is not likely to produce condensation product, i.e. solidification compound, to assemble well.
The present invention is to solve the invention of the above subject, that is, the present invention provides [1] below~[18].
[1] a kind of solidification compound contains ingredient below:
(A) monomer containing 1 or more carbon-to-carbon unsaturated bond,
(B) carbon black, and
(C) curing agent；
Relative to 100 mass parts of the ingredient (A), the ingredient (B) is contained with 5 mass parts~45 mass parts range.
[2] solidification compound according to [1], wherein the ingredient (A) contains following compositions (A1).
Ingredient (A1): contain the monomer of 1 or more (methyl) acryloyl group
[3] solidification compound according to [2], wherein the ingredient (A1) containing following compositions (A1-1) and At least one of (A1-2).
Ingredient (A1-1): the monomer with 1 (methyl) acryloyl group
Ingredient (A1-2): the monomer with 2 or more (methyl) acryloyl groups
[4] solidification compound according to [3], wherein relative to 100 mass parts of the ingredient (A1), with 40 matter Amount part~100 mass parts range contains the ingredient (A1-2).
[5] solidification compound according to any one of [1]~[4], wherein further contain following compositions (A’)。
Ingredient (A '): there is the polymer of the Component units from the ingredient (A)
[6] solidification compound according to [5], wherein the ingredient (A ') is with from (methyl) third The polymer of the Component units of the monomer of enoyl-.
[7] solidification compound according to [5] or [6], wherein the ingredient (A ') has cross-linked structure.
[8] solidification compound according to any one of [5]~[7], wherein the ingredient (A ') has average grain The particle shape that 1 μm~100 μm of diameter.
[9] solidification compound according to any one of [1]~[8], wherein further contain following compositions (B’)。
Ingredient (B '): calcining at least one of silica sand and graphite
[10] solidification compound according to [9], wherein the ingredient (B ') is calcining silica sand,
Relative to 100 mass parts of ingredient (A), which is contained with 10 mass parts~300 mass parts range.
[11] solidification compound according to [9], wherein the ingredient (B ') is graphite,
Relative to 100 mass parts of ingredient (A), which is contained with 0.5 mass parts~10 mass parts range.
[12] solidification compound according to [1]~[11], wherein further contain inorganic filler.
[13] solidification compound according to [12], wherein inorganic filler be selected from silica filler, glass filler and At least one of glass fibre.
[14] solidification compound according to any one of [1]~[13], wherein further contain lower shrinkage Agent.
[15] a kind of formed body is obtained from solidifying solidification compound described in any one of [1]~[14].
[16] formed body according to [15], wherein formed body be kitchen basin, table top (カ ウ ン タ ー ト ッ プ) or Washbowl.
[17] a kind of manufacturing method of formed body, including preparing the process (a) of solidification compound and combining curability Object is solidified to form the process (b) of formed body,
Wherein, the solidification compound at least contains ingredient below:
(A) monomer containing 1 or more carbon-to-carbon unsaturated bond,
(B) carbon black, and
(C) curing agent；
Relative to 100 mass parts of the ingredient (A), the ingredient (B) is contained with 5 mass parts~45 mass parts range.
[18] manufacturing method of the formed body according to [17], wherein process (b) includes the heating at 100 DEG C or more The lower process by solidification compound compression forming 1 minute~50 minutes.
According to other main points, the present invention provides [21] below~[26].
[21] a kind of solidification compound contains ingredient below:
The agglomerate (bulk) that (2A) includes at least the monomer containing 1 or more carbon-to-carbon unsaturated bond forms composition,
(2B) is selected from any one of calcining silica sand, graphite and carbon black or two or more combinations, and
(C) curing agent,
When the ingredient (2B) is only carbon black, relative to 100 mass parts of ingredient (2A), with 15 mass parts~30 mass parts Range contains the carbon black,
When the ingredient (2B) is carbon black and calcining any one of silica sand or graphite or two or more combinations, relative to 100 mass parts of ingredient (2A) contain the carbon black with 30 range below the mass.
[22] solidification compound according to [21], wherein ingredient (2A) further contains to have to come from and contain The polymer of the Component units of the monomer of carbon-to-carbon unsaturated bond.
[23] solidification compound according to [21] or [22], wherein ingredient (2A) further contains lower shrinkage Agent.
[24] a kind of formed body is obtained from solidifying solidification compound described in any one of [21]~[23].
[25] a kind of manufacturing method of formed body, including preparing the process of solidification compound and consolidating solidification compound The process changed and form formed body,
Wherein, the solidification compound at least contains ingredient below:
The agglomerate that (2A) includes at least the monomer containing 1 or more carbon-to-carbon unsaturated bond forms composition,
(2B) is selected from any one of calcining silica sand, graphite and carbon black or two or more combinations, and
(C) curing agent；
When the ingredient (2B) is only carbon black, relative to 100 mass parts of ingredient (2A), with 15 mass parts~30 mass parts Range contains the carbon black,
When the ingredient (2B) is carbon black and calcining any one of silica sand or graphite or combination of more than two kinds, relative to 100 mass parts of ingredient (2A) contain the carbon black with 30 range below the mass.
[26] manufacturing method of the formed body according to [25], wherein solidification compound is made to be solidified to form molding The process of body includes under 100 DEG C or more of heating by the process of solidification compound compression forming 1 minute~50 minutes.
According to the present invention, the solidification compound that can assemble well is provided.According to the present invention, it provides and is suitable for manufacturing The manufacturing method of above-mentioned formed body.
Specific embodiment
[solidification compound]
Hereinafter, being illustrated to solidification compound of the invention.
In this specification, " (methyl) acryloyl group " is made with the meaning for including " acryloyl group " and " methylacryloyl " With, can for they one or both of." (methyl) acryloyl group " be " acryloyl group " and " methylacryloyl " this two When person, by total quantity as (methyl) acryloyl group of these groups.
Solidification compound of the invention contains ingredient below:
(A) monomer (hereinafter, sometimes referred to as " ingredient (A) ") containing 1 or more carbon-to-carbon unsaturated bond,
(B) carbon black (hereinafter, sometimes referred to as " ingredient (B) "), and
(C) curing agent (hereinafter, sometimes referred to as " ingredient (C) ")；
Relative to 100 mass parts of ingredient (A), mentioned component (B) is contained with 5 mass parts~45 mass parts range.
Ingredient (A) is the compound that resin is capable of forming by solidification.
By containing ingredient (A), the solidification compound with mobility can be obtained.In addition, can will be of the invention Solidification compound is shaped to the formed body of desired size or shape.
Mentioned component (A) preferably comprises selected from the monomer in molecular structure containing 1 carbon-to-carbon unsaturated bond and contains 2 At least one of the monomer of a above carbon-to-carbon unsaturated bond more preferably includes the monomer containing 1 carbon-to-carbon unsaturated bond With the monomer containing 2 or more carbon-to-carbon unsaturated bonds.
In a mode, mentioned component (A), which preferably comprises to be selected from molecular structure, contains 1 carbon-to-carbon unsaturated bond Monomer and containing at least one of 2 or more monomers of carbon-to-carbon unsaturated bond, and relative to 100 mass of ingredient (A) Part, it include the monomer containing 2 or more carbon-to-carbon unsaturated bonds with 40 mass parts~100 mass parts range.
As ingredient (A), such as the monomer containing 1 or more (methyl) acryloyl group can be enumerated (hereinafter, sometimes referred to as " ingredient (A1) ")；The styrenic monomers such as styrene, α-methylstyrene, α-butylstyrene；Acrylonitrile, metering system The unsaturated nitriles such as nitrile；The simple functions such as maleic anhydride, phenyl maleimide, N-cyclohexylmaleimide, vinyl acetate Unsaturated monomer；Divinylbenzene, diallyl phthalate etc. have the monomer of multiple carbon-to-carbon unsaturated bonds.
Ingredient (A) preferably comprises ingredient (A1), more preferably ingredient (A1).
Ingredient (A1) can be containing the monomer being selected from 1 (methyl) acryloyl group (hereinafter, sometimes referred to as " ingredient (A1-1) " in the monomer (hereinafter, be sometimes referred to as " ingredient (A1-2) ")) and with 2 or more (methyl) acryloyl groups extremely Few one kind.
As ingredient (A1-1), such as (methyl) acrylic acid can be enumerated；(methyl) methyl acrylate, (methyl) acrylic acid (methyl) propyl acrylates such as ethyl ester, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Zhong Ding (methyl) butyl acrylates such as ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2- second The own ester of base, (methyl) lauryl acrylate etc. have (methyl) acrylate of the alkyl of carbon atom number 1~15；(methyl) propylene Sour tetrahydrochysene chaff ester, (methyl) isobornyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate etc. have ring-type (methyl) acrylate of structure；(methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxyl Base butyl ester etc. has (methyl) acrylate of hydroxy alkyl；(methyl) allyl acrylate etc. has 1 (methyl) acryloyl The monomer of base and carbon-to-carbon double bond (wherein, not including (methyl) acryloyl group).As ingredient (A1-1), it is preferable to use having (methyl) acrylate of the alkyl of carbon atom number 1~15 more preferably uses (methyl) methyl acrylate.
As ingredient (A1-2), preferably with the monomer of 2~6 (methyl) acryloyl groups.
Ingredient (A1-2) can be monomer shown in following formula (1) or (2).
CH2=CH-CO-O- (CmH2m- O)n- CO-CH=CH2 (1)
CH2=CCH3- CO-O- (CmH2m- O)n- CO-CCH3=CH2 (2)
In formula (1) and (2), m indicates that 1~10 integer, n indicate 1~15 integer.When n is 2 or more, there are multiple (CmH2m- O) it may be the same or different.
From reducing in the polymerization since the viscosity of monomer is got higher and issuable unreacted (methyl) acryloyl From the viewpoint of base, ingredient (A1) preferably strand it is short, m be preferably 1~6, n be preferably 1~14, n be more preferably 1~8, n into One step is preferably 1~5.
As monomer shown in the formula (1) of m=2 or (2), such as ethylene glycol two (methyl) acrylic acid of n=1 can be enumerated Ester, diethylene glycol two (methyl) acrylate of n=2, triethylene glycol two (methyl) acrylate of n=3, n=4 tetrem two Alcohol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate (for example, n=6~14).
From reducing in the polymerization since the viscosity of monomer is got higher and issuable unreacted (methyl) acryloyl From the viewpoint of base, the preferred strand of monomer shown in the formula (1) of m=2 or (2) is short, and n is preferably 1~5.
As monomer shown in the formula (1) of m=3 or (2), such as propylene glycol two (methyl) acrylic acid of n=1 can be enumerated Ester, dipropylene glycol two (methyl) acrylate of n=2, the tripropylene glycol two (methyl) acrylate of n=3, n=6~14 it is poly- Propylene glycol two (methyl) acrylate.
As monomer shown in the formula (1) of n=1 or (2), such as ethylene glycol two (methyl) acrylic acid of m=2 can be enumerated Ester, 1,3 butylene glycol two (methyl) acrylate of m=4, the neopentyl glycol two (methyl) acrylate of m=5, m=6 1, The 1,10- last of the ten Heavenly stems two of 6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate of m=9, m=10 Alcohol two (methyl) acrylate.
From reducing in the polymerization since the viscosity of monomer is got higher and issuable unreacted (methyl) acryloyl From the viewpoint of base, the preferred strand of monomer shown in the formula (1) of n=1 or (2) is short, and m is preferably 1~10, more preferably 1~ 6。
In monomer shown in formula (1) or formula (2), the preferred monomer of the monomer of m=2 or n=1.
Ingredient (A1-2) can be monomer shown in following formula (3) or (4).
(HO-CH2)4-k- C- (CH2- O-CO-CH=CH2)k (3)
(HO-CH2)4-k- C- (CH2- O-CO-CCH3=CH2)k (4)
In formula (3) and (4), k indicates 2~4 integer.
As monomer shown in formula (3) or (4), such as the pentaerythrite three (methyl) acrylate of k=3, k=can be enumerated 4 pentaerythrite four (methyl) acrylate.
Ingredient (A1-2) can be monomer shown in following formula (5) or (6).
(CH2=CH-CO-O-CH2)r- C (CH2OH)3-r- CH2OCH2- C (CH2OH)3-q(CH2O-CO-CH =CH2)q (5)
(CH2=CCH3- CO-O-CH2)r- C (CH2OH)3-r- CH2OCH2- C (CH2OH)3-q(CH2O-CO- CCH3=CH2)q (6)
In formula (5) and (6), q and r each independently represent 1~3 integer.
As monomer shown in formula (5) or (6), such as dipentaerythritol four (methyl) propylene of q=2 and r=2 can be enumerated Acid esters, the dipentaerythritol five (methyl) acrylate of q=3 and r=2, q=3 and r=3 dipentaerythritol six (methyl) third Olefin(e) acid ester.
Ingredient (A1-2) can be monomer shown in following formula (7) or (8).
CH3- CH2- C (CH2OH)3-p(CH2O-CO-CH=CH2)p (7)
CH3- CH2- C (CH2OH)3-p(CH2O-CO-CCH3=CH2)p (8)
In formula (7) and (8), p indicates 1~3 integer.
As monomer shown in formula (7) or (8), such as trimethylolpropane tris (methyl) acrylic acid of p=3 can be enumerated Ester.
Ingredient (A1-2) can be monomer shown in following formula (9) or (10).
(CH2=CH-COO-CH2)s- C (C2H5)3-s- CH2OCH2- C (C2H5)3-t(CH2O-CO-CH= CH2)t (9)
(CH2=CCH3- COO-CH2)s- C (C2H5)3-s- CH2OCH2- C (C2H5)3-t(CH2O-CO-CCH3= CH2)t (10)
In formula (9) and (10), s and t each independently represent 1~3 integer.
As monomer shown in formula (9) or (10), such as two (trimethylolpropane) four (first of s=2 and t=2 can be enumerated Base) acrylate.
In monomer with 3 or more (methyl) acryloyl groups, monomer with 3 (methyl) acryloyl groups and have 4 The monomer of a (methyl) acryloyl group since viscosity is not too high, reactive reduction is not likely to produce in polymerization reaction, It is not easy (methyl) acrylate of remained unreacted, therefore preferably.
From reducing in the polymerization since the viscosity of monomer is got higher and issuable unreacted (methyl) acryloyl From the viewpoint of base, ingredient (A1-2) more preferably ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylic acid Ester, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, 1,6-HD two (methyl) propylene Acid esters, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) third Olefin(e) acid ester.
As ingredient (A1-2), further preferred neopentyl glycol two (methyl) acrylate, ethylene glycol two (methyl) propylene Acid esters, trimethylolpropane tris (methyl) acrylate.
If reducing unreacted (methyl) acryloyl group, it is capable of forming the formed body with close cross-linked structure. Therefore, pass through and mentioned component (A1-2) be added and reduces unreacted (methyl) acryloyl group, make solidification compound solidify and Obtained formed body has close cross-linked structure, and the surface hardness for the formed body that can be improved.
Mentioned component (A1-1) and mentioned component (A1-2) can use individually, and can also combine a variety of and make With.
From the viewpoint of the aggregation for improving solidification compound, ingredient (A1) preferably comprises ingredient (A1-2).Relative to 100 mass parts of ingredient (A1) preferably contain ingredient (A1-2) with 17 mass parts~100 mass parts range, more preferably with 20 matter Amount part~100 mass parts range contains ingredient (A1-2), is further preferably contained with 40 mass parts~100 mass parts range Have ingredient (A1-2), ingredient (A1-2) is more preferably contained with 40 mass parts~91 mass parts range, particularly preferably with 67 Mass parts~83 mass parts range contains ingredient (A1-2).
In a mode, ingredient (A1) preferably comprises ingredient (A1-1) and ingredient (A1-2).In solidification of the invention In property composition, for (A1-1) and ingredient (A1-2), by quality ratio, preferably with ingredient (A1-1): ingredient (A1-2) Contain for the range of 1:1~1:10, is more preferably contained with the range of 1:2~1:5.
Solidification compound of the invention can be further containing the polymer with the Component units from ingredient (A) (hereinafter, sometimes referred to as " polymer " or " ingredient (A ') ").
By containing ingredient (A '), it is able to suppress the tacky, i.e. sticky of solidification compound of the invention.This such hair Bright solidification compound can aid in the mouldability for improving formed body, the formed body of intended shape especially easy to form. In the present specification, " viscosity " refers to be attached to the substance of surrounding after, be not easy to remain on the property of the substance of surrounding when leaving. Contain ingredient (A ') by solidification compound, the appearance of formed body obtained from enabling the solidification compound to solidify becomes Well.
Ingredient (A ') can have from the Component units as ingredient (A) monomer illustrated.Ingredient (A ') can be independent Containing the Component units for coming from mentioned component (A), can also combine containing there are many Component units for coming from ingredient (A).
As ingredient (A '), the material with the Component units from following monomer can be enumerated, the monomer is with (first Base) acryloyl group monomer；For example, the benzene such as alpha-alkyl phenylethylenes such as styrene, α-methylstyrene, α-butylstyrene Vinyl monomer；The unsaturated nitriles such as acrylonitrile, methacrylonitrile；Maleic anhydride, phenyl maleimide, cyclohexyl Malaysia acyl The unsaturated monomer of the simple functions such as imines, vinyl acetate；Divinylbenzene, diallyl phthalate etc. have multiple The monomer etc. of carbon-to-carbon unsaturated bond.Ingredient (A ') can individually contain the Component units from foregoing illustrative monomer, can also Contain the Component units from multiple monomers with combination.
Ingredient (A ') is preferably with the Component units from the monomer with (methyl) acryloyl group.As with (methyl) The monomer of acryloyl group can enumerate the monomer illustrated as ingredient (A1).
Ingredient (A ') contains to come with 80 mass parts~100 mass parts range preferably with respect to 100 mass parts of ingredient (A ') From the Component units of the above-mentioned monomer with (methyl) acryloyl group.
In a mode, ingredient (A ') is free of from other monomers in addition to the monomer with (methyl) acryloyl group Component units.That is, in this mode, ingredient (A ') is only by the Component units structure from the monomer with (methyl) acryloyl group At.
Ingredient (A ') preferably has cross-linked structure.When with cross-linked structure, ingredient (A ') is preferably comprised selected from from ingredient (A1-2) Component units and there are multiple carbon-to-carbon unsaturated bonds from divinylbenzene, diallyl phthalate etc. At least one of Component units of monomer.
In ingredient (A '), preferably with respect to 100 mass parts of ingredient (A '), contained with 0.1 mass parts~20 mass parts range There are the Component units from the monomer that can constitute cross-linked structure.
As the manufacturing method of ingredient (A '), such as emulsion polymerization, suspension polymerisation, dispersin polymerization can be enumerated etc. and generate particle The polymerization of the polymer of shape, the method for crushing the cross-linked polymer obtained by other polymerizations, specifically, can Enumerate the method recorded in Japanese Unexamined Patent Publication 5-155907 bulletin.
Ingredient (A ') preferably has particle shape.The average grain diameter of ingredient (A ') is preferably in 1 μm~100 μm of range, more It is preferred that in 20 μm~50 μm of range.By using such ingredient (A '), molding obtained by being formed using solidification compound The appearance of body is less prone to the shape of ingredient (A '), and the appearance of formed body can become good.By using such ingredient (A ') can reduce the hardness of formed body obtained by forming using solidification compound or the unevenness of scratch resistance.It is above-mentioned average Partial size be accumulate 50% weight partial size, can use optical diffraction scattering particle size determination machine (Malvern corporation, Mastersizer it) is measured.
Ingredient (A ') can be contained relative to 100 mass parts of ingredient (A) with 10 mass parts~40 mass parts range, can To be contained with 15 mass parts~35 mass parts range.By containing ingredient (A ') with above-mentioned range, it is able to suppress the present invention Solidification compound viscosity.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, preferably with 1 mass parts~10 The range of mass parts contains ingredient (A '), more preferably contains ingredient (A ') with 2 mass parts~7 mass parts range.By above The range stated contains ingredient (A '), is able to suppress the viscosity of solidification compound of the invention.It should be noted that in this specification In, to " ingredient (A), ingredient (B), ingredient (C), ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic filler, reinforcing material, For the total amount of pigment and auxiliary agent ", ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic filler, strengthening material are selected from existing In the case where at least one of material, pigment and auxiliary agent ingredient, refer to the existing ingredient, ingredient (A), ingredient (B) and ingredient (C) total amount；It is not present in ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent In the case where, refer to the total amount of ingredient (A), ingredient (B) and ingredient (C).For lower shrinkage agent, ingredient (B), ingredient (B '), Ingredient (C), inorganic filler, reinforcing material, pigment and auxiliary agent, are described below.
In solidification compound of the invention, preferably with ingredient (A): the mass ratio of ingredient (A ') is 1.5:1~5:1's Range contains ingredient (A) and ingredient (A '), more preferably contains ingredient (A) and ingredient (A ') with the range of 2.0:1~4.5:1.On Stating ingredient (A) is, for example, ingredient (A1).
Solidification compound of the invention can further contain lower shrinkage agent.Lower shrinkage agent can aid in inhibition Inprocess shrinkage when solidification compound being made to solidify and form.
As lower shrinkage agent, such as polystyrene, polyvinyl acetate, polymethyl methacrylate, acid can be enumerated and changed Property saturated polymers or their copolymer such as polystyrene, the modified polyvinyl acetate of acid, modified polyvinyl acetate.As Above-mentioned copolymer can enumerate vinyl acetate styrene copolymer, copolymer of methyl methacrylatestyrene.As altogether Polymers is, it is preferable to use block copolymer.They can be used alone, and also two or more kinds may be used.
As lower shrinkage agent, it is preferable to use styrene-vinyl acetate copolymer, methyl methacrylate-benzene second The block copolymers such as alkene copolymer.By containing such lower shrinkage agent, solidification compound can be assembled well, and energy Enough inhibit the viscosity on the surface of solidification compound.By the solidification compound molding that will assemble well, can obtain To the desired formed body of no crackle etc..It should be noted that in the present specification, solidification compound, SMC or BMC can be good Assembling well indicates that the surface of solidification compound, SMC or BMC are not easy to do, in other words, in equably wet state, no Can be partially dried, and solidification compound, SMC or BMC are not likely to produce condensation product.It the case where as condensation product is not likely to produce, can It enumerates tiny granular substance and is not easy the case where separating from solidification compound.For representative, refer to apply mechanical external force, Such as when mechanical stirring or mixing, it is capable of forming 1 block with the surface in wet state.
As lower shrinkage agent, styrene-vinyl acetate copolymer is more preferably used.By using such low receipts Contracting agent can reduce viscosity when preparing solidification compound of the invention.It can be good by such solidification compound Ground mixing, can disperse well ingredient contained in solidification compound.Especially using solidification compound as SMC or BMC is in use, SMC or BMC can assemble well.For such solidification compound, the preparation energy of solidification compound Enough become easy.
Solidification compound largely containing inorganic fillers such as silica fillers is not easy to assemble sometimes.However, passing through curability Composition contains lower shrinkage agent as described above, can reduce viscosity when preparing solidification compound.In such situation Under, even if largely containing inorganic filler, solidification compound can also be assembled well.
Such solidification compound can aid in be formed with good hardness, for example good scratch resistance at Type body.
When above-mentioned copolymer is contained from the Component units of 2 kinds of monomers, the quality of 2 kinds of monomers contained in the copolymer Than the range that can be 5:95~95:5.When more specifically, using vinyl acetate styrene copolymer, acetic acid second is come from The Component units of enester: the Component units from styrene can be the range of 5:95~30:70 by quality ratio, can also be with For the range of 5:95~15:85.When using copolymer of methyl methacrylatestyrene, the structure from methyl methacrylate At unit: the Component units from styrene can be the range of 5:95~15:85 by quality ratio.
For example, relative to 100 mass parts of ingredient (A) lower shrinkage can be contained with 5 mass parts~30 mass parts range Agent can contain lower shrinkage agent with 10 mass parts~30 mass parts range, can be with 10 mass parts~25 mass parts model It encloses containing lower shrinkage agent, lower shrinkage agent can be contained with 12 mass parts~20 mass parts range.By with above-mentioned model Enclose containing lower shrinkage agent, solidification compound can be assembled well, and be able to suppress solidification compound surface it is viscous Property.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, preferably with 0.5 mass parts~ The range of 8 mass parts contains lower shrinkage agent, more preferably contains lower shrinkage agent with 1 mass parts~6 mass parts range, into one Step preferably contains lower shrinkage agent with 1.5 mass parts~5 mass parts range.By in solidification compound with above-mentioned model The solidification compound that contributes to form and can assemble well containing lower shrinkage agent is enclosed, and is able to suppress curability combination The viscosity on the surface of object.For ingredient (B), ingredient (B '), ingredient (C), inorganic filler, reinforcing material, pigment and auxiliary agent, rear Face is described.
For lower shrinkage agent, the styrene solution containing the 30 mass % lower shrinkage agents can be in 25 DEG C of viscosity The range of 0.2~5.0Pas.
Ingredient (B) and the ingredient below (B ') that can be added as needed are the chemical combination that can aid in the coloring of formed body Object.
Ingredient (B '): calcining at least one of silica sand and graphite
Ingredient (B) can be amorphous carbon.Ingredient (B) can be irregular made of the multiple set of primary particle and complicated Shape condensate (aggregate structure or structured configurations).Above-mentioned primary particle can be for example partial size be 10nm~ The particle of 100nm.The primary particle size of ingredient (B) can be used electron microscope and be measured.Ingredient (B) can be non-laminar knot The carbon compound of structure.
The average grain diameter of ingredient (B) for example can be 1nm~100nm, or 10nm~90nm.Average grain diameter is for example It can be measured by electron microscope observation.
Ingredient (B) can be the substance for not being activated processing.
As ingredient (B), substance usually used in the art can be used.As ingredient (B), such as can enumerate Mitsubishi Carbon Black (Mitsubishi chemical Co., Ltd's system), SUNBLACK (Asahi Carbon Co. Ltd. system), (East Sea Tokablack Society of Carbon Co., Ltd. system).
In a mode, as ingredient (B), the powder being only made of carbon black can be used.
In a mode, ingredient (B) can be to make charcoal blacks, i.e. carbon black dispersion using surfactant or resin State uses.As charcoal blacks, such as the mixture of carbon black and acrylic resin, carbon black and polystyrene resin can be enumerated Mixture.As such charcoal blacks, Black SHPA-865 (firmly changing colored Co. Ltd. system) etc. can be enumerated.
Calcining silica sand, i.e. color sand refers to using silica sand or silica grain as aggregate, and makes inorganic pigment calcining coloring in them Surface made of silica sand.Calcining silica sand for example can be for natural silica, corundum, basalt, sandstone or volcanic ash float stone etc. Then the calcining silica sand pigment such as special processing ceramic device inorganic pigment in the surface of silica sand uses the high-temperature smelting pots such as rotary kiln Colored aggregate made of calcining fusion, i.e. smalt are carried out at such as 800 DEG C.
The silica sand that can be used in being formed calcining silica sand contains crystallinity silica, usually removes SiO2In addition, also containing Al, The impurity such as Fe.Above-mentioned silica sand contains the SiO of 97 mass parts or more preferably with respect to 100 mass parts of silica sand2, further preferably 98 matter Measure the SiO of part or more2。SiO2Content Si amount can be measured by using ICP emission spectroanalysis method and measure.
As the calcining silica sand pigment that can be used in being formed calcining silica sand, ware inorganic pigment, ceramics can be enumerated Pigment etc..
Calcining silica sand can for example pass through the table to silica sands such as natural silica, corundum, basalt, sandstone, volcanic ash float stones Special processing ceramic device inorganic pigment in face etc. calcines silica sand pigment, and will be contour using rotary kiln through the silica sand of special processing Warm smelting furnace carries out calcining fusion at for example, about 800 DEG C to manufacture.
The calcining silica sand that medium particle diameter is 10 μm~4000 μm can be used for example in calcining silica sand.Here, medium particle diameter is adopted With the partial size obtained as follows, i.e. measurement utilizes the residual component on the sieve after the sieve screening of JIS specification standards, sieve residual component accumulation Frequency (%) becomes 50% partial size.
As calcining silica sand, such as Shinto Color Sand (Xin Dongtao expects Co. Ltd. system), Color can be enumerated Sand (gloomy this native mining industry institute corporation in mountain), Color Sand (Co., Ltd.'s ball east system).
Graphite is the mineral only consisting of carbon, and has the platelike crystal for belonging to hexagonal crystal system.Graphite has layer structure.Stone Ink can have graphene face structure or graphene layer structure.
Solidification compound through the invention contains graphite, though make the solidification compound solidify obtained from In the case that the surface of type body generates any damage, the situation that the damaged portion appears as white can be also efficiently reduced, It is preferably able to the situation for preventing the damaged portion from appearing as white.It is thought that because the hardness of graphite is low, it is forming In the case that the surface of body generates damage, the graphite for being present in the surface is crushed, and is able to suppress the unrestrained of the light on the surface of formed body Reflection.Solidification compound through the invention contains graphite, and the appearance of the formed body formed by the solidification compound can Become good.For example, the coloring on the surface of above-mentioned formed body can become well, the surface of especially formed body is not likely to produce portion Divide the position for appearing as white.
The medium particle diameter of graphite is, for example, 1 μm~1000 μm, can be 2 μm~100 μm.Medium particle diameter is used and is obtained as follows Partial size, that is, measurement using JIS specification standards sieve screening after sieve on residual component, sieve residual component cumulative frequency (%) As 50% partial size.
As graphite, such as CP, J-CPB, CB-100, ACP, ACB-100, J-SP, SP-5030 (Japan can be enumerated Graphite Co. Ltd. system).
In a mode, relative to 100 mass parts of ingredient (B), can be with the carbon black that the state of charcoal blacks is added 10 mass parts~100 mass parts range.The method from carbon black can be well dispersed into solidification compound in terms of Consideration is advantageous.In a mode, the carbon black in solidification compound is added to from the viewpoint of improving productivity, it can Charcoal blacks are not made in above range.
In solidification compound of the invention, relative to 100 mass parts of ingredient (A), with 5 mass parts~45 mass parts Range contains ingredient (B).If the content of ingredient (B) is excessive, it cannot get the curability that can assemble well combination sometimes Object.If the content of ingredient (B) is very few, the bad order of the formed body formed sometimes using solidification compound is good.In addition, By containing ingredient (B) and ingredient (A), ingredient (B) can be well dispersed into solidification compound of the invention.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can with 0.6 mass parts with On range contain ingredient (B), can be contained with ranges more than 0.8 mass parts ingredient (B), can be with 1 mass parts more than Range contains ingredient (B), can be contained with 12 ranges below the mass ingredient (B), can be with 10 ranges below the mass Containing ingredient (B), it can be contained with 7 ranges below the mass ingredient (B), can be contained with 6.5 ranges below the mass Ingredient (B).
In a mode, in solidification compound of the invention, relative to 100 mass parts of ingredient (A), such as can be with Contain ingredient (B) with ranges more than 10 mass parts, can be contained with ranges more than 18 mass parts ingredient (B), it can be with 20 Ranges more than mass parts contains ingredient (B), can be contained with ranges more than 30 mass parts ingredient (B).Relative to ingredient (A) 100 mass parts, such as can be contained with 40 ranges below the mass ingredient (B).For example, relative to 100 mass of ingredient (A) Part, ingredient (B) can be contained with 18 mass parts~45 mass parts range, it can be with the model of 20 mass parts~40 below the mass It encloses containing ingredient (B), ingredient (B) can be contained with 30 mass parts~40 mass parts range.Contain ingredient with above-mentioned range (B) solidification compound can be assembled well.The appearance of the formed body formed using the solidification compound can become Well.Even if can also efficiently reduce the damaged portion in the case where the surface of formed body generates any damage and seem For the situation of white, it is preferably able to the situation for preventing the damaged portion from appearing as white.
In the above method, in solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), Ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can be with Contain ingredient (B) with ranges more than 0.6 mass parts, can be contained with ranges more than 0.8 mass parts ingredient (B), it can be with 1 Ranges more than mass parts contains ingredient (B), can be contained with 12 ranges below the mass ingredient (B), can be with 10 mass Part range below contains ingredient (B), can be contained with 7 ranges below the mass ingredient (B), can be with 6 below the mass Range contain ingredient (B).In this mode, in solidification compound of the invention, relative to ingredient (A), ingredient (B), Ingredient (C), ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 matter of total amount Part is measured, ingredient (B) can be contained with 2 mass parts~12 mass parts range, can be contained with 3 mass parts~10 mass parts range There is ingredient (B), ingredient (B) can be contained with 3 mass parts~7 mass parts range, it can be with 4 mass parts~7 mass parts model It encloses containing ingredient (B), ingredient (B) can be contained with 5 mass parts~7 mass parts range.
In the past, it in the formed body, particularly saturate formed body formed using solidification compound, is forming sometimes The position that the surface of body generates hickie, appears as white in surface generation part.So, it is not easy to it is good to provide appearance Formed body.
In contrast, the solidification compound of the method uses curability group by containing ingredient (B) with above-mentioned range Good appearance can be had by closing the formed body that object is formed, and be especially able to suppress to generate on the surface of the formed body and partially seen Come for the position of white.
In the past, in the case where the surface of formed body generates any damage, the damaged portion appears as white sometimes.So And ingredient (B) is contained by the solidification compound of the method, even if the case where the surface of formed body generates any damage Under, the situation that damaged portion as described above appears as white can be also efficiently reduced, is preferably able to prevent damaged portion Appear as the situation of white.It is thought that above-mentioned damaged portion is also strong because containing ingredient (B) by solidification compound It colours strongly.
In the above method, it by containing ingredient (B) and ingredient (A), is formed using solidification compound of the invention Formed body in, ingredient (B) can disperse well.As a result, the appearance of the formed body can become good.By with above-mentioned Range contain ingredient (B), the solidification compound that can assemble well can be obtained.It is combined using the curability of the method The appearance for the formed body that object is formed can become good.For example, the coloring on the surface of the formed body can become well, can press down The surface portion of formed body processed appears as the generation at the position of white.Even if generating any damage on the surface of the formed body In the case of, the situation that the damaged portion appears as white can be also efficiently reduced, is preferably able to prevent the damaged portion from seeing Get up for the situation of white.
Relative to 100 mass parts of ingredient (A), calcining silica sand is preferably contained with ranges more than 10 mass parts, more preferably with Ranges more than 40 mass parts contains calcining silica sand, further preferably contains calcining silica sand with ranges more than 80 mass parts, more Calcining silica sand is further preferably contained with ranges more than 90 mass parts, even more preferably with ranges more than 100 mass parts Contain calcining silica sand.Relative to 100 mass parts of ingredient (A), calcining silica sand is preferably contained with 300 range below the mass, more It is preferred that containing calcining silica sand with 250 range below the mass, calcining is further preferably contained with 200 range below the mass Silica sand.Relative to 100 mass parts of ingredient (A), calcining silica sand can be contained with 10 mass parts~300 mass parts range, it can be with Contain calcining silica sand with 40 mass parts~300 mass parts range, can be contained with 80 mass parts~300 mass parts range and be forged Silica sand is burnt, calcining silica sand can be contained with 90 mass parts~250 mass parts range, it can be with 100 mass parts~250 mass parts Range contain calcining silica sand.By containing calcining silica sand in solidification compound with above-mentioned range, the curability is used The appearance for the formed body that composition is formed can become good.For example, the coloring on the surface of formed body can become well, especially It is to be not likely to produce the position that part appears as white on the surface of formed body.Even if generating any damage on the surface of formed body In the case where, the situation that the damaged portion appears as white can be also efficiently reduced, is preferably able to prevent the damaged portion Appear as the situation of white.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can with 10 mass parts with On range contain calcining silica sand, calcining silica sand can be contained with ranges more than 15 mass parts, can be with 60 below the mass Range contain calcining silica sand, calcining silica sand can be contained with 40 ranges below the mass.It is combined in curability of the invention In object, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic filler, enhancing 100 mass parts of total amount of material, pigment and auxiliary agent can contain calcining silicon with such as 10 mass parts~60 mass parts range More specifically sand can contain calcining silica sand with 15 mass parts~40 mass parts range.Curability group through the invention It closes object and calcining silica sand is contained with above-mentioned range, the appearance of the formed body formed by the solidification compound can become good. For example, the coloring on the surface of formed body can become well, part especially is not likely to produce on the surface of formed body and is appeared as The position of white.Even if can also efficiently reduce the damaged portion in the case where the surface of formed body generates any damage The situation for appearing as white is preferably able to the situation for preventing the damaged portion from appearing as white.
Relative to 100 mass parts of ingredient (A), graphite is preferably contained with ranges more than 0.1 mass parts, more preferably with 0.5 Ranges more than mass parts contains graphite, further preferably contains graphite with ranges more than 1 mass parts, particularly preferably with 2 matter Range more than amount part contains graphite.Relative to 100 mass parts of ingredient (A), stone is preferably contained with 10 range below the mass Ink more preferably contains graphite with 7.5 range below the mass, further preferably contains graphite with 5 range below the mass, Graphite is particularly preferably contained with 3 range below the mass.Relative to 100 mass parts of ingredient (A), can with 0.1 mass parts~ The range of 10 mass parts contains graphite, can contain graphite with 0.5 mass parts~10 mass parts range, can be with 0.5 mass The range of part~7.5 mass parts contains graphite, can contain graphite with 1 mass parts~5 mass parts range, can be with 2 mass The range of part~3 mass parts contains graphite.Solidification compound through the invention contains graphite with above-mentioned range, is consolidated by this The appearance for the formed body that the property changed composition is formed can become good.For example, the coloring on the surface of formed body can become well, Especially the position that part appears as white is not likely to produce on the surface of formed body.Even if being generated on the surface of formed body any In the case where damage, the situation that the damaged portion appears as white can be also efficiently reduced, is preferably able to prevent the damage Part appears as the situation of white.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can with 0.1 mass parts with On range contain graphite, graphite can be contained with ranges more than 0.2 mass parts, can be contained with 2 ranges below the mass There is graphite, graphite can be contained with 1 range below the mass.In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, graphite can be contained with such as 0.1 mass parts~2 mass parts range, more specifically, can be with 0.2 mass parts~1 mass parts range contains graphite.Graphite is contained with above-mentioned range by solidification compound, uses this The appearance for the formed body that the solidification compound of invention is formed can become good.For example, the coloring on the surface of formed body can Become good, is especially not likely to produce the position that part appears as white on the surface of formed body.In addition, even if in formed body Surface generate any damage in the case where, can also efficiently reduce the situation that the damaged portion appears as white, preferably It can prevent the damaged portion from appearing as the situation of white.
When containing ingredient (B ') in solidification compound, relative to 100 mass parts of ingredient (A), can with 5 mass parts~ The range of 45 mass parts contains ingredient (B), can contain ingredient (B) with 5 mass parts~40 mass parts range.
By containing ingredient (B) with above-mentioned range, the solidification compound that can assemble well is obtained.Pass through solidification Property composition contains ingredient (B) with above-mentioned range, and the appearance of the formed body formed using the solidification compound can become Well.For example, the coloring on the surface of formed body can become well, especially by containing ingredient (B) in solidification compound It is to be able to suppress to generate the position that part appears as white on the surface of formed body.Even if being generated on the surface of formed body any In the case where damage, the situation that the damaged portion appears as white can be also efficiently reduced, is preferably able to prevent the damage Part appears as the situation of white.
In aforesaid way in solidification compound containing ingredient (B '), in solidification compound, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can be contained with ranges more than 0.5 mass parts ingredient (B), can be with 12 ranges below the mass Ingredient (B) can be contained ingredient (B) with 10 ranges below the mass, can contain ingredient with 8 ranges below the mass (B), it can be contained with 7 ranges below the mass ingredient (B), can be contained with 6 ranges below the mass ingredient (B).? In the method, in solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can be with such as 0.5 mass The range of part~12 mass parts contains carbon black, more specifically, can contain charcoal with 0.5 mass parts~10 mass parts range It is black, carbon black can be contained with 0.5 mass parts~8 mass parts range, can be contained with 0.6 mass parts~7 mass parts range Carbon black can contain carbon black with 0.6 mass parts~6 mass parts range.It, can by containing ingredient (B) with above-mentioned range Obtain the solidification compound that can assemble well.By containing ingredient (B), formed using solidification compound of the invention The appearance of formed body can become good.Even if, also can be effective in the case where the surface of formed body generates any damage Ground reduces the situation that damaged portion appears as white, is preferably able to the situation for preventing damaged portion from appearing as white.
In a mode, ingredient (B) and ingredient (B ') is applied in combination, as above-mentioned (B '), uses calcining silica sand.At this In mode, relative to 100 mass parts of ingredient (A), ingredient (B) can be contained with 20 mass parts~40 mass parts range, it can be with Contain ingredient (B) with 30 mass parts~40 mass parts range；Ingredient (B ') can contain relative to 100 mass parts of ingredient (A) 10 mass parts~300 mass parts can contain 100 mass parts~250 mass parts.According to the method, calcines silica sand and be colored as Black, therefore, the coloring on the surface of formed body can become well, to be especially not likely to produce damage on the surface of formed body, i.e., Make to generate damage, can also efficiently reduce the situation that the damaged portion appears as white, be preferably able to prevent the pars affecta Divide the situation for appearing as white.
In a mode, ingredient (B) and ingredient (B ') is applied in combination, as above-mentioned (B '), uses graphite.In the method In, relative to 100 mass parts of ingredient (A), ingredient (B) can be contained with 5 mass parts~40 mass parts range, it can be with 5 matter Amount part~10 mass parts range contains ingredient (B)；Relative to 100 mass parts of ingredient (A), 0.5 mass parts~10 can be contained The ingredient (B ') of mass parts, can be containing 0.5 mass parts~7.5 mass parts ingredient (B '), can be with 1 mass parts~5 mass The range of part contains ingredient (B '), can contain ingredient (B ') with 2 mass parts~3 mass parts range.Graphite is due to its hardness It is low, it is therefore contemplated that the graphite for being present in the surface crushes, the table of formed body in the case where the surface of formed body generates damage The diffusing reflection of the light in face is inhibited.Therefore, in this mode, even if the content of ingredient (B) is less range, keep this solid In the case that the surface of formed body obtained from the property changed composition solidifies generates any damage, which is also not easy to be identified For the damaged portion of white.The coloring on the surface of the formed body can become well, to be especially not easy on the surface of the formed body Generate the position that part appears as white.
Ingredient (C) plays a role as the initiator that ingredient (A) is carried out free radical polymerization.As ingredient (C), such as lift 1,1 '-azos bis- (hexamethylene -1- formonitrile HCNs), 2,2 '-azos bis- (2,4,4- trimethylpentenes), 2,2 '-azos are double out (2- methylpropane), 2- cyano -2- propylazoformamide, 2,2 '-azos bis- (2- hydroxy-propionic acid methyl esters), 2, 2 '-azos bis- (2- methyl-butanenitriles), 2,2 '-azobis isobutyronitriles, 2,2 '-azos bis- (2,4- dimethyl-pentanenitriles), Bis- [the 2- (2- imidazoline -2- base) third of 2,2 '-azos bis- (2,4- dimethyl -4- methoxyl-valeronitriles), 2,2 '-azos Alkane], the azo-compounds such as bis- (2 Methylpropionic acid) dimethyl esters of 2,2 '-azos；Cumyl peroxide, tert-butyl peroxide are different The diacyl peroxides such as propyl benzene, peroxide di-t-butyl, benzoyl peroxide, lauroyl peroxide, dialkyl group series initiators； Peroxidating -3,3,5- trimethylhexanoate, the peroxylauric acid tert-butyl ester, peroxidating tert-butyl isobutyrate, peroxidating Tert-butyl acetate, peroxidating hexahydro terephthalic acid di tert butyl carbonate, peroxidating azelaic acid di tert butyl carbonate, peroxidating -2- ethyl Hecanoic acid t-butyl ester, peroxidating -2 ethyl hexanoic acid 1,1,3,3- tetramethyl butyl ester, peroxidating -2 ethyl hexanoic acid tert-pentyl ester, The peroxyesters series initiators such as the peroxidating pivalic acid tert-butyl ester；Peroxidating allylic carbon tert-butyl acrylate, isopropyl peroxide carbonic acid The peroxocarbonates series initiators such as tert-butyl ester；1,1- cyclohexane di-tert-butyl peroxide, di-tert-butyl peroxide -3,3 1,1-, The ketal peroxides series initiators such as 5- trimethyl-cyclohexane, bis- tert-hexyl peroxide -3,3,5- trimethyl-cyclohexane of 1,1- Deng.They may be used alone, can also be used in combination.
10 hours half life temperatures of ingredient (C), i.e. half-life period are preferably 60 DEG C or more of temperature of 10 hours, more preferable 80 DEG C or more, additionally, it is preferred that 130 DEG C hereinafter, more preferable 120 DEG C or less.
100 mass of total amount in solidification compound of the invention, relative to ingredient (A), ingredient (B) and ingredient (C) Part, preferably contained ingredient (C) with 0.1 mass parts~0.6 mass parts range, more preferably with 0.2 mass parts~0.5 mass parts Range contains ingredient (C), further preferably contains ingredient (C) with 0.2 mass parts~0.45 mass parts range.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, preferably comprise 0.03 mass The ingredient (C) of part~3.0 mass parts, further preferably 0.05 mass parts~2.0 mass parts ingredient (C).For inorganic Filler, reinforcing material, pigment and auxiliary agent are described below.
Solidification compound of the invention can further contain inorganic filler.By containing inorganic filler, can be improved Using the heat resistance for the formed body that solidification compound of the invention is formed, the hardness of formed body, scratch resistance can become good It is good.
As inorganic filler, it is preferable to use insoluble in ingredient (A) and its polymerization and cured inorganic filler, example will not be hindered Silica filler, aluminium hydroxide, aluminium oxide, calcium carbonate, calcium silicates, calcium sulfate, magnesium hydroxide, talcum, bentonite can such as be enumerated Clay, glass filler, glass fibre.It is preferred that inorganic filler be in silica filler, glass filler and glass fibre at least One kind, more preferably at least one of silica filler and glass filler and glass fibre.Inorganic filler can be particle shape Shape, or threadiness.
Silica filler is to contain filler of the crystallinity silica as principal component.Silica filler usually removes SiO2In addition also Contain the impurity such as Al, Fe.Contain crystallinity silica as the silica filler of principal component relative to 100 mass of silica filler Part, preferably comprise the SiO of 97 mass parts or more2, more than further preferably 99 mass parts SiO2。SiO2Content can pass through Si amount is measured using ICP emission spectroanalysis method and is found out.Contain silica filler by solidification compound, using of the invention The hardness on the surface for the formed body that solidification compound is formed, scratch resistance can become good.For example, the surface of the formed body Mohs' hardness can be 3 or more.
Silica filler is preferably shape of particle.The range that average grain diameter is such as 1 μm~30 μm can be used in silica filler Silica filler, more specifically, can be used average grain diameter be 2 μm~20 μm range silica filler.Here, average grain Diameter refers to the median particle diameter based on volume reference, is to measure the value measured by laser diffraction and scattering formula grain size analysis.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts 100 mass parts of total amount of contracting agent, ingredient (B '), silica filler, reinforcing material, pigment and auxiliary agent, preferably with 30 mass parts~ The range of 80 mass parts contains silica filler, more preferably contains silica filler with 30 mass parts~75 mass parts range, into one Step preferably contains silica filler with 35 mass parts~70 mass parts range.
Glass filler is to contain filler of the amorphism silica as principal component.Glass filler is by with Si atom and its The glass of its metallic atom is constituted.As above-mentioned other metallic atoms, Al, Ca, Mg, Zr, Na, Sr and Zn etc. can be enumerated.
Glass can contain Si atom and other metallic atoms of more than two kinds.As glass, such as can enumerate containing SiO2 With the glass of other metal oxides.As SiO2Metal oxide in addition can enumerate Al2O3、CaO、MgO、ZrO2、Na2O、 SrO and ZnO etc..Glass can contain SiO2With other metal oxides of more than two kinds.Contain amorphism silica as master The glass filler of ingredient contains the SiO of 60 mass parts or more preferably with respect to 100 mass parts of glass filler2。SiO2Content can be with Si amount is measured by using ICP emission spectroanalysis method and is found out.
Glass filler can further contain B2O3、F2Equal ingredients.As glass filler, it can be used together and form different 2 kinds Above glass filler.
As glass filler, the glass filler of granular form can be used.The median particle diameter of glass filler is preferably 1 μm~ 20 μm of range, more preferably 1 μm~10 μm of range, further preferably 3 μm~10 μm of range.
It is in above-mentioned range by the median particle diameter of glass filler, the mobility of solidification compound can become better It is good.Such solidification compound can aid in form the formed body with superior scratch resistance.In glass filler Value partial size can be measured by laser diffractometry.Specifically, size distribution can be measured according to JIS Z8825, what is obtained In the cumulative distribution of volume reference, partial size is accumulated by 50%, i.e. d50 value is set to median particle diameter.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts 100 mass parts of total amount of contracting agent, ingredient (B '), glass filler, reinforcing material, pigment and auxiliary agent, preferably with 30 mass parts~ The range of 80 mass parts contains glass filler, more preferably contains glass filler with 30 mass parts~75 mass parts range, into one Step preferably contains glass filler with 35 mass parts~70 mass parts range.
The glass fibre for the range that average fiber length is 0.5mm~30mm can be used for example in glass fibre, can also be with Use the glass fibre for the range that average fiber length is 1mm~15mm.Glass fibre is the glass fibre with fibre morphology. As the material of glass fibre, such as alkali glass and alkali-free glass can be enumerated.Average fiber length can be applied in combination in glass fibre Spend different glass fibres of more than two kinds.
The glass fibre that average diameter is 5 μm~20 μm can be used for example in glass fibre.
For glass fibre, surface can be surface-treated.As the surface treatment, such as it can enumerate and utilize silicon The processing of alkane coupling agent.As the functional group on the surface for being present in glass fibre after surface treatment, vinyl, epoxy can be enumerated Base, styryl, (methyl) acryloyl group, amino, isocyanurate group, urea groups, sulfydryl, thioether group, isocyanate group etc..From From the aspect of the boundary strength for further increasing resin and glass fibre contained in formed body, above-mentioned functional group is preferably second Alkenyl, styryl, (methyl) acryloyl group or sulfydryl.
Relative to 100 mass parts of ingredient (A), glass fibre can be contained with 10 mass parts~80 mass parts range, it can To contain glass fibre with 20 mass parts~70 mass parts range.
Relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), lower shrinkage agent, ingredient (B '), glass filler, 100 mass parts of total amount of reinforcing material, pigment and auxiliary agent can contain 1 mass parts~30 mass parts glass fibre.
By the way that inorganic filler is added, the resistance to of formed body obtained from solidifying solidification compound of the invention can be improved Hot, the scratch resistance of formed body becomes well, and by the way that glass fibre is added, the impact resistance of formed body can further become Well.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can with 30 mass parts with On range contain inorganic filler, inorganic filler can be contained with ranges more than 35 mass parts, can be with 40 mass parts more than Range contain inorganic filler, inorganic filler can be contained with ranges more than 55 mass parts, can be with 60 mass parts more than Range contains inorganic filler, can contain inorganic filler with ranges more than 65 mass parts；It can be with 85 models below the mass It encloses containing inorganic filler, inorganic filler can be contained with 80 ranges below the mass, it can be with 77 ranges below the mass Contain inorganic filler.In solidification compound, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), lower shrinkage Agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can be with 35 mass parts~85 The range of mass parts contains inorganic filler, can contain inorganic filler with 40 mass parts~85 mass parts range, can be with 55 Mass parts~80 mass parts range contains inorganic filler, can contain inorganic fill out with 65 mass parts~77 mass parts range Material.By containing inorganic filler with above-mentioned range, the resistance to of formed body obtained from solidifying solidification compound can be improved The viscosity of solidification compound can be adjusted to the range being easily processed, the behaviour of solidification compound by hot and scratch resistance Making performance enough becomes good.
In solidification compound of the invention, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), low receipts Contracting agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, preferably with 30 mass parts~ The range of 80 mass parts contains at least one of silica filler and glass filler (hereinafter, sometimes referred to as " ingredient (d) "), more excellent Choosing contains at least one of silica filler and glass filler with 30 mass parts~75 mass parts range, further preferably with 35 Mass parts~70 mass parts range contains.For reinforcing material, pigment and auxiliary agent, described below.By with above-mentioned Range contain ingredient (d), can be improved the heat resistance and scratch resistance of formed body obtained from solidifying solidification compound, The viscosity of solidification compound can be adjusted to the range being easily processed, the operability of solidification compound can become good It is good.
In solidification compound of the invention, content ratio, i.e. ingredient (d)/glass fibre of ingredient (d) and glass fibre It is preferably 3/1~100/1, more preferably 4/1~80/1, particularly preferably 5/1~30/1 in terms of quality criteria.Pass through ingredient (d) with the content of glass fibre than in above-mentioned range, the mobility of solidification compound can become better, being easy will The solidification compound is shaped to desired formed body.
In a mode, in solidification compound of the invention, inorganic filler be glass fibre and glass filler or Person's silica filler, and relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), lower shrinkage agent, ingredient (B '), glass 100 mass parts of total amount of filler or silica filler, glass fibre, reinforcing material, pigment and auxiliary agent, with 2 mass parts~20 mass The range of part contains glass fibre.
Solidification compound of the invention can further contain reinforcing material.As reinforcing material, such as dimension can be enumerated Synthetic fibre fiber, acrylic fiber.They can be used a kind or reinforcing material of more than two kinds be applied in combination.Reinforcing material can have Help improve solidify solidification compound obtained from formed body impact resistance.
For example, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), lower shrinkage agent, ingredient (B '), inorganic 100 mass parts of total amount of filler, reinforcing material, pigment and auxiliary agent can use enhancing with 1 mass parts~30 mass parts range Material.
Solidification compound of the invention can further contain pigment.Here, pigment is used for the coloring of formed body, refer to Ingredient in addition to ingredient (B) and ingredient (B ').As such pigment, such as titanium oxide, calcium carbonate, barium sulfate can be enumerated. Preferred pigments are titanium oxide.
In solidification compound of the invention, for example, relative to ingredient (A), ingredient (B), ingredient (C), ingredient (A '), Lower shrinkage agent, ingredient (B '), inorganic filler, reinforcing material, pigment and auxiliary agent 100 mass parts of total amount, can be with 0.1 mass The range of part~12 mass parts contains pigment.
Solidification compound of the invention can further contain crosslinked rubber particles.
By containing crosslinked rubber particles, the impact resistance of formed body obtained from solidifying solidification compound of the invention Performance enough becomes good.Contain crosslinked rubber particles, the operability of solidification compound of the invention by solidification compound It can become good, which can be mixed well.For example, solidification compound of the invention is made When SMC or BMC, the operability of SMC or BMC can become good.Especially when BMC is made, which can be mixed well It closes, the aggregation of BMC can become good.
The average grain diameter of the primary particle of crosslinked rubber particles is preferably the range of 50nm~500nm, more preferably 70nm The range of~300nm.The average grain diameter of above-mentioned primary particle can measure observed grain by dyeing the section of formed body Son diameter and find out.
Crosslinked rubber particles can be by with constituting from the polyfunctional monomer with 2 or more carbon-to-carbon unsaturated bonds The material of unit is formed.As the above-mentioned polyfunctional monomer with 2 or more carbon-to-carbon unsaturated bonds, such as maleic acid can be enumerated Diallyl, (methyl) allyl acrylate, divinylbenzene, trivinylbenzene, aklylene glycol two (methyl) acrylate, Isocyanic acid triallyl, polyethylene glycol two (methyl) acrylate.They can be used only a kind, can also be applied in combination 2 kinds with On.
Crosslinked rubber particles can be by with from selected from monomer, butadiene, isoamyl two with (methyl) acryloyl group The Component units of at least one kind of monomer in alkene, chlorobutadiene, styrene, alpha-alkyl phenylethylene, acrylonitrile and methacrylonitrile It is formed with the material of the Component units from the above-mentioned polyfunctional monomer with 2 or more carbon-to-carbon double bonds.
As the monomer with (methyl) acryloyl group, such as it can enumerate and exist as ingredient (A1-1) or ingredient (A1-2) Foregoing illustrative monomer.Monomer with (methyl) acryloyl group is preferably (methyl) alkyl acrylate.
As (methyl) alkyl acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate can be enumerated；(methyl) Isopropyl acrylate etc. (methyl) propyl acrylate；(methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) third (methyl) butyl acrylates such as olefin(e) acid isobutyl ester, (methyl) tert-butyl acrylate；(methyl) 2-EHA；(first Base) lauryl acrylate；(methyl) tetrahydrofurfuryl acrylate；(methyl) isobornyl acrylate；(methyl) benzyl acrylate； More specifically (methyl) cyclohexyl acrylate etc. can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) isobutyl acrylate, (first Base) tert-butyl acrylate, (methyl) 2-EHA and (methyl) cyclohexyl acrylate.
As alpha-alkyl phenylethylene, such as α-methylstyrene, t-butyl styrene can be enumerated.
Crosslinked rubber particles can be the rubber particles of single layer, or the rubber of the multilayer with 2 or more layers Particle.It is preferred that crosslinked rubber particles are the rubber particles of multilayer.
It is preferred that crosslinked rubber particles are by constituting selected from the material that is made of rubber-like polymer and by glassy polymers At least one of material material is formed.As the material being made of rubber-like polymer, such as can enumerate containing 50 mass % The material of Component units from acrylate above, as the material being made of glassy polymers, such as can enumerate containing The material of Component units of the 50 mass % or more from methacrylate.
Acrylate is preferably the acrylate with the alkyl of carbon atom number 1~8, such as can enumerate the positive fourth of acrylic acid Ester, 2-EHA.
Methacrylate is preferably the methacrylate with the alkyl of carbon atom number 1~8, such as can enumerate methyl Methyl acrylate, ethyl methacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, The secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate and cyclohexyl methacrylate.
Hereinafter, the layer formed by the material constituted with rubber-like polymer or part are known as " soft layer " sometimes, it will be by The layer or part formed with the material that glassy polymers is constituted is known as " hard layer ".That is, above-mentioned crosslinked rubber particles are by being selected from The formation of at least one of soft layer and hard layer.
Soft layer can also be by further containing from least one kind of in styrene, isoprene and chlorobutadiene The material of the Component units of monomer is formed.
Hard layer can be by further containing from acrylate, α-first selected from the alkyl with carbon atom number 1~4 The material of the Component units of at least one kind of monomer in base styrene, t-butyl styrene, acrylonitrile and methacrylonitrile is formed. As the acrylate of the alkyl with carbon atom number 1~4, n-butyl acrylate can be enumerated.
In a preferred manner, crosslinked rubber particles are the rubber particles of multilayer, further preferably by least having core portion With the coating in covering core portion, and at least one of above-mentioned core portion and above-mentioned coating are by having from 2 or more The material of the Component units of the polyfunctional monomer of carbon-to-carbon unsaturated bond is formed.It is more with 2 or more carbon-to-carbon unsaturated bonds Functional monomer is as described above.Above-mentioned core portion refers to the part for being present in the bosom of particle.
Core portion is preferably by the material with the Component units from the polyfunctional monomer with 2 or more carbon-to-carbon unsaturated bonds Material is formed.Form the polyfunctional monomer unit contained in the material in above-mentioned core portion with 2 or more carbon-to-carbon unsaturated bonds Content preferably can be 0.0001 mass parts~10 mass parts range relative to 100 mass parts of material for forming core portion.
Core portion can be formed by any one of hard layer and soft layer.Above-mentioned coating can be by hard layer and soft layer Any one of formed.For example, above-mentioned core portion can be formed by hard layer, above-mentioned coating can be formed by soft layer.
Coating is preferably formed by the material with the Component units from the monomer with (methyl) acryloyl group.As The monomer recorded as ingredient (A1) can be used, specifically, propylene can be used in monomer with (methyl) acryloyl group Sour methyl esters, methyl methacrylate, butyl acrylate etc. have (methyl) acrylate of the alkyl of carbon atom number 1~4, (first Base) allyl acrylate.
In a mode, the material for constituting coating can further contain the Component units from styrene.That is, constituting The material of coating can have the Component units from the monomer with (methyl) acryloyl group and the composition from styrene Unit.In this mode, coating is preferably formed by soft layer.
In a mode, coating be rubber cross particle outermost layer, further preferably without from have 2 with The Component units of the polyfunctional monomer of upper carbon-to-carbon unsaturated bond do not have cross-linked structure more preferably.Contain here, outermost layer refers to Have to form the layer of the material of the particle surface of rubber cross particle.That is, outermost layer be far from particle bosom and existing layer. In this mode, crosslinked rubber particles have core portion and coating, which is outermost layer.In this mode, core portion is preferred It is formed by 1 layer.
In a mode, coating includes the outermost layer of the 1st coating of the 1st coating and covering in covering core portion.On The 1st coating can directly be covered by stating outermost layer, can also cover the 1st coating in a manner of being situated between and be equipped with other layers.Core portion and Outermost layer is as described above.
In this mode, crosslinked rubber particles be preferably be respectively provided with 1 layer or more soft layer and hard layer have two Layer or more rubber particles.
In the mode, crosslinked rubber particles are preferably that the soft layer for being respectively provided with 1 layer or more and hard layer have Three layers or more of crosslinking rubber granule.The crosslinked rubber particles of the method from inhibit processing and forming when heat deterioration, because heating caused by Rubber particles deformation, especially improve formed body heat resistance from the viewpoint of be advantageous.It should be noted that in crosslinking rubber There are when the hard layer of 2 layers or more of soft layer or 2 layers or more in particle, each soft layer or each hard layer can be respectively by identical Material formed, can also be formed from different materials, such as be formed from different materials.
The crosslinked rubber particles of the method preferably successively have core portion, middle layer and outermost from the center of particle outward The structure of layer.For core portion and outermost layer, as described above.Middle layer is the layer being present between core portion and outermost layer, for example, Above-mentioned 1st coating.Middle layer can have 2 layers or more of layer.In the crosslinked rubber particles of the method, core portion and outermost layer It can be formed, can also be formed by hard layer by soft layer, middle layer can be formed by soft layer, can also be by hard layer shape At can also be formed by the laminated body of soft layer and hard layer.
The structure of crosslinked rubber particles as the method, such as can enumerate from the center of particle outward successively by soft Layer-hard layer-soft layer-hard layer, soft layer-hard layer-hard layer, soft layer-soft layer-hard layer, hard Layer-soft layer-hard layer, hard layer-hard layer-soft layer-hard layer, hard layer-soft layer-hard layer-are hard The structure that matter layer is formed.It is preferred that above structure is from the center of particle outward successively by hard layer-soft layer-hard layer shape At three-decker, the four-layer structure that is formed by hard layer-hard layer-soft layer-hard layer or by hard layer-it is soft The four-layer structure that layer-hard layer-hard layer is formed.
The crosslinked rubber particles of the method are preferably core portion and outermost layer is formed by hard layer, middle layer is formed by soft layer Three-decker rubber particles.It is formed by core portion and outermost layer by hard layer, is able to suppress the deformation of crosslinked rubber particles. It is formed by middle layer by soft layer, can be improved the toughness of crosslinked rubber particles.
In this mode, outermost layer does not preferably have from the polyfunctional monomer with 2 or more carbon-to-carbon unsaturated bonds Component units, more preferably formed by hard layer.Further preferred above-mentioned outermost layer be by have selected from methyl methacrylate, The copolymer that the material of at least two kinds of Component units in methyl acrylate and ethyl acrylate is formed.Above-mentioned outermost layer is especially excellent Choosing is formed by the material with the Component units from methyl methacrylate and methyl acrylate.
In this mode, core portion is preferably by with from the polyfunctional monomer with 2 or more carbon-to-carbon unsaturated bonds The hard layer of Component units is formed.
In this mode, more officials contained in the material in above-mentioned core portion with 2 or more carbon-to-carbon unsaturated bonds are formed The content of energy monomeric unit preferably can be 0.0001 mass parts~10 mass relative to 100 mass parts of material for forming core portion The range of part.
In this mode, more preferable core portion is by with selected from from multifunctional with 2 or more carbon-to-carbon unsaturated bonds The Component units of monomer, the Component units of methacrylate from the alkyl with carbon atom number 1~4 and from having carbon At least one kind of material in the Component units of the acrylate of the alkyl of atomicity 1~4 is formed.Above-mentioned core portion is relative to formation 100 mass parts of material in core portion, such as can be contained with 0.01 mass parts~10 mass parts range from 2 or more The Component units of the polyfunctional monomer of carbon-to-carbon unsaturated bond, such as can be contained with 60 mass parts~99.99 mass parts range There are the Component units of the methacrylate of the alkyl as the methyl methacrylate with carbon atom number 1~4, such as The alkyl as the methyl acrylate with carbon atom number 1~4 can be contained with 0 mass parts~30 mass parts range The Component units of acrylate.Particularly preferred above-mentioned core portion is by with from more officials with 2 or more carbon-to-carbon unsaturated bonds The material of the Component units of energy monomer, methyl methacrylate and methyl acrylate is formed, particularly preferably by comprising from 2 The material shape of the Component units of the polyfunctional monomer of a above carbon-to-carbon unsaturated bond, methyl methacrylate and methyl acrylate At.
In this mode, preferred interlayer is by with from the polyfunctional monomer with 2 or more carbon-to-carbon unsaturated bonds The materials of Component units formed, more preferably by with from the polyfunctional monomer with 2 or more carbon-to-carbon unsaturated bonds The hard layer of Component units is formed.
In this mode, being formed has the more of 2 or more carbon-to-carbon unsaturated bonds contained in the material of above-mentioned middle layer The content of functional monomer's unit preferably can be 0.0001 mass parts~10 relative to 100 mass parts of material for forming middle layer The range of mass parts.
In this mode, more preferable middle layer is by with selected from from more officials with 2 or more carbon-to-carbon unsaturated bonds It can the Component units of monomer, the Component units of acrylate from the alkyl with carbon atom number 1~8 and from styrene At least one kind of material in Component units is formed.Middle layer, such as can be with relative to 100 mass parts of material for forming middle layer Contain the structure from the polyfunctional monomer with 2 or more carbon-to-carbon unsaturated bonds with 0.01 mass parts~10 mass parts range At unit, such as it can be contained with 40 mass parts~99.99 mass parts range there is as the n-butyl acrylate carbon The Component units of the acrylate of the alkyl of atomicity 1~8 can be contained with 0 mass parts~50 mass parts range from benzene The Component units of ethylene.Particularly preferred above-mentioned middle layer is by having from having the multifunctional of 2 or more carbon-to-carbon unsaturated bonds The material of the Component units of monomer, n-butyl acrylate and styrene is formed, particularly preferably by comprising from 2 or more The material of the Component units of the polyfunctional monomer of carbon-to-carbon unsaturated bond, n-butyl acrylate and styrene is formed.
In this mode, in above-mentioned crosslinked rubber particles, for thickness and the outermost thickness in core portion and middle part Than for example, the thickness in core portion and middle part: outermost thickness is preferably 20:1~5:1 in primary particle.
Solidification compound of the invention can further contain viscosity reductant (auxiliary agent).
As viscosity reductant, such as the surfactant of phosphate type can be enumerated.As the surfactant of phosphate type, example Polyxyethylated (carbon atom number 12~15) ether phosphate such as can be used.
Solidification compound of the invention can further contain release agent, ultraviolet absorbing agent, dyestuff, Inhibition of polymerization Agent, chain-transferring agent, antioxidant, fire retardant etc..
As release agent, such as phosphoric acid polyester, lead stearate, calcium stearate, zinc stearate can be illustrated.
Enumerate BTA system, triazine system, benzoic ether system, salicylate system, cyano can be used for example in ultraviolet absorbing agent Acrylic ester, oxanilide system or benzophenone series.
As polymerization inhibitor, such as the phenols such as quinones, hydroquinones, p-tert-Butylcatechol can be enumerated.
As chain-transferring agent, such as the alkyl sulfides such as tert-butyl mercaptan, n octylmercaptan, n-dodecyl mercaptan can be enumerated Alcohol；The aromatic mercaptans such as benzenethiol, thionaphthol；Thioacetic acid；Thioacetic acid monooctyl ester, ethylene glycol two (mercaptoacetate), three hydroxyls The alkyl thioglycollates such as methylpropane three (mercaptoacetate), pentaerythrite four (mercaptoacetate)；β-mercaptopropionic acid；β- The mercaptan compounds such as the Arrcostab of mercaptopropionic acid.They can be used alone, alternatively, it is also possible to it is appropriately combined using two kinds with On.
As antioxidant, such as 6- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) third oxygen can be enumerated Base] -2,4,8,10- tetra-tert dibenzo [d, f] [1,3,2] twoPhosphorus cycloheptane, 2,2 '-di-2-ethylhexylphosphine oxide [6- (2H- benzotriazole -2- base) -4- (1,1,3,3- tetramethyl butyl) phenol].
[formed body]
Hereinafter, being illustrated to formed body of the invention.
Formed body of the invention is formed by solidification compound of the invention.
Formed body of the invention can be used for kitchen utensils, sanitary use etc., such as kitchen basin, table top or can wash Washbowl.
Hereinafter, being illustrated to an example of the manufacturing method for the manufacture for being suitable for formed body of the invention.
Above-mentioned manufacturing method includes the process of solidification compound of the preparation containing ingredient (A), ingredient (B) and ingredient (C) (a) and solidification compound is made to be solidified to form the process (b) of formed body,
Relative to 100 mass parts of mentioned component (A), mentioned component (B) is contained with 5 mass parts~45 mass parts range.
Process (a) is the process for preparing the solidification compound of the invention containing ingredient (A), (B) and (C).
Process (a) can for example be carried out in 40 DEG C~50 DEG C of temperature range.
In a mode, process (a) may include mixture of the preparation containing ingredient (A), (B) and (C), and this is mixed The temperature range that object is closed at such as 40 DEG C~80 DEG C stands such as 1 hour~6 hours, prepares solidification compound.Pass through by Such process, the solidification compound after being viscosified.The method is advantageous when using compression forming methods in process (b) 's.
Above-mentioned operation (a) may include being kneaded the mixture containing ingredient (A), (B) and (C).Above-mentioned mixing can To use such as kneader, kneading extruder (Kneader-Ruder), single axle extruding machine, biaxial extruder, planetary mixing Machine, Trimix mixing machine, Henschel mixer.
In a mode, process (a) may include preparation and be kneaded the mixture containing ingredient (A), (B) and (C), make Standby solidification compound.
In a mode, process (a) may include that mixture of the preparation containing ingredient (A), (B) and (C) then will The mixture is kneaded, and thus prepares solidification compound.
In a mode, process (a) may include preparation and be kneaded the mixture containing ingredient (A), (B) and (C), and Temperature range by the mixture at such as 40 DEG C~80 DEG C stands such as 1 hour~6 hours, prepares solidification compound.
In a mode, process (a) may include 1st mixture of the preparation containing ingredient (A), (B) and (C), by this 1st mixture is kneaded and forms the 2nd mixture, further that the 2nd mixture is quiet in such as 40 DEG C~80 DEG C of temperature range It sets such as 1 hour~6 hours, prepares solidification compound.
The preparation of solidification compound in process (a) can modulate each ingredient in a single stage, can also gradually add Each ingredient is added to be prepared with multiple stages.
In process (a), each ingredient, such as ingredient (A), which can according to need, to be dissolved or dispersed in other ingredients and is added.
In a mode, above-mentioned solidification compound further contains ingredient (A ').
In this mode, process (a) may include the acrylic syrup that preparation has ingredient (A) and ingredient (A ') (Acrylic syrup) is modulated the acrylic syrup and ingredient (B) and (C).The method can from ingredient (A ') It is advantageous from the aspect of being well dispersed into solidification compound.
Solidification compound obtained in process (a) for example can be liquid or solid-like.Solidification compound is solid When shape, which for example can be SMC or BMC.It is excellent in process (a) when solidification compound is SMC or BMC Choosing includes the mixture of preparation and mixing containing ingredient (A), (B) and (C).
Process (b) is the process for making solidification compound obtained in process (a) be solidified to form formed body.
Preferable process (b) may include so that solidification compound is solidified to form formed body using compression forming methods.
As compression forming methods, commonly used approach in the technical field can be used.
In a preferred manner, process (b) includes that solidification compound is made to be solidified to form molding using compression forming methods Body.That is, process (b) carries out heating and compression forming to solidification compound obtained in process (a), consolidate solidification compound Change and formed body can be formed.If being able to easily form the formed body of complicated shape using the method.If using we Formula, the then dimensional accuracy of the formed body obtained can become good.If using the method, the surface of obtained formed body Flatness is easy to become good.
In this mode, more specifically, the solidification compound as SMC or BMC can be configured and is having a pair In the mold of upper mold and lower mold, the heating and compression forming of SMC or BMC are carried out under elevated pressure, form formed body.
In this mode, as long as heating temperature can carry out the cured temperature of solidification compound, preferably with than The high temperature of 10 hours half life temperatures of ingredient (C) carries out, and is more preferably carried out with 100 DEG C or more of temperature.Heating temperature is excellent Choosing is than ingredient contained in the solidification compounds such as the unsaturated monomer containing 1 or more carbon-to-carbon unsaturated bond or ingredient (A ') Decomposition temperature it is low, such as can 150 DEG C or less, more particularly, in 140 DEG C or less carry out.
In this mode, compression usually carries out under the pressure of 3MPa~12MPa.
In this mode, it heats and the time of compression forming for example can be 1 minute~50 minutes.
In this mode, process (b) preferably make solidification compound 100 DEG C or more cured under heating 1 minute~50 Minute, form formed body.
Embodiment
Hereinafter, being described in detail using embodiment to the present invention, but the present invention is not limited to this.
(embodiment 1-1)
Listed in Table 1 mass parts are added following in the dual-arm kneader (Toshin Co. Ltd. system) of capacity 1L Ingredient.
Methyl methacrylate (hereinafter, sometimes referred to as " MMA ")
Neopentylglycol dimethacrylate (FA-125M, Hitachi Chemical Co., Ltd.'s system.Hereinafter, sometimes referred to as “NPG”)
Polymer is (by having of manufacturing of the method recorded in Japanese Unexamined Patent Publication 5-155907 bulletin from having The crosslinking structural body of the Component units of the monomer of (methyl) acryloyl group)
Pigment masterbatch (masterbatch of the polystyrene resin of the carbon black containing 30 weight % and 70 weight %)
Curing agent (Kayacarbon (registered trademark) BIC-75, KAYAKUAKZO Co. Ltd. system)
Lower shrinkage agent (styrene-vinyl acetate block copolymer, MODIPER SV10B, Japan Oil Co System)
Viscosity reductant (DISPER BYK-111, BYK Chemie Japan Co. Ltd. system)
Silica filler (Seichin superfine No.4, ball kettle kettle family pottery material Co. Ltd. system, 6 μm of average grain diameter)
Glass fibre (ECS03-670, Central Glass Fiber Co. Ltd. system, fibre length 3mm, fiber 13 μm of diameter)
Then, it carries out being kneaded for 40 minutes, obtains solidification compound.
Obtained solidification compound is enclosed into aluminium bag.The aluminium bag is stood 3 hours in 60 DEG C of hot-air drying stove.So Afterwards, aluminium bag is taken out from drying oven, is cooled to room temperature, obtains claylike solidification compound (BMC).
(embodiment 1-2)
Other than carbon black (Sigma Aldrich system) is further added, material identical with embodiment 1-1 is used Material.The ratio of each ingredient is changed in a manner of becoming mass ratio recorded in table 1.Progress is similarly operated with embodiment 1-1, Obtain claylike solidification compound (BMC).
(embodiment 1-3)
In addition to be further added calcining silica sand (MP Black, Co., Ltd.'s ball east system) other than, using with embodiment 1-2 Identical material.Shown in being recorded in the such as table 1 of the quality of each ingredient contained in solidification compound.It carries out and embodiment 1-1 Same operation, obtains claylike solidification compound (BMC).
(embodiment 1-4 and 1-5)
In addition to graphite (J-CPB, Japanese blacklead Co. Ltd. system) or graphite (SP-5030, Japanese blacklead is further added Co. Ltd. system) other than, use material identical with embodiment 1-1.The mass ratio of each ingredient contained in solidification compound As shown in being recorded in table 1.Progress is similarly operated with embodiment 1-1, obtains claylike solidification compound (BMC).
Comparative example 1-1
The ratio of each ingredient is changed in a manner of becoming mass ratio recorded in table 1.It carries out same as embodiment 1-1 Operation, obtains claylike solidification compound (BMC).
(comparative example 1-2)
The ratio of each ingredient is changed in a manner of becoming mass ratio recorded in table 1.It carries out same as embodiment 1-1 Operation, obtains claylike solidification compound (BMC).
The ingredient being added in embodiment and comparative example and respective mass parts are shown, it is opposite to show carbon black in table 2 in table 1 The ratio of 100 mass parts of solidification compound formed in embodiment or comparative example.In table 1, "-" expression is not added.
[table 1]
[table 2]
(embodiment 2-1~2-3)
It in addition to without using polymer, is carried out similarly with embodiment 1-1~embodiment 1-3, obtains curability combination Object (BMC).In addition, the ratio of each material is the value recorded in table 3.
(comparative example 2-1)
In addition to without using polymer, it is carried out similarly with comparative example 1-2, obtains solidification compound (BMC).In addition, The ratio of each material is the value recorded in table 3.
The material being added in embodiment 2-1~2-3, comparative example 2-1 and respective mass parts, table 4 are shown in table 3 In ratio of the carbon black relative to 100 mass parts of solidification compound formed in embodiment or comparative example is shown.In table 3, "-" Expression is not added.
[table 3]
[table 4]
(embodiment 3-1)
Except using 1,6-Hexanediol dimethacrylate (village Xin Zhong chemistry system: hereinafter, sometimes referred to as " HD-N ") generation It other than NPG, is carried out similarly with embodiment 1-1, obtains solidification compound (BMC).In addition, the ratio of each material is table 5 The value of middle record.
(embodiment 3-2)
In addition to the ratio of each material is changed to the value recorded in table 5, it is carried out similarly with embodiment 1-2, consolidate The property changed composition (BMC).
The ingredient being added in embodiment 3-1 and 3-2 and respective mass parts are shown in table 5, carbon black phase is shown in table 7 For the ratio of 100 mass parts of solidification compound formed in embodiment.In table 5, "-" expression is not added.
[table 5]
(embodiment 4-1)
It is carried out similarly, is solidified with embodiment 1-1 in addition to this using each material with the ratio recorded in table 6 Property composition (BMC).
(embodiment 4-2)
In addition to NPG is used only and replaces MMA and NPG, it is carried out similarly with embodiment 1-1, obtains solidification compound (BMC).In addition, the ratio of each material is the value recorded in table 6.
The ingredient being added in embodiment 4-1~4-2 and respective mass parts are shown in table 6, carbon black phase is shown in table 7 For the ratio of 100 mass parts of solidification compound formed in embodiment.In table 6, "-" expression is not added.
[table 6]
[table 7]
(aggregation of BMC is evaluated)
The state of BMC obtained in following evaluation embodiment and comparative example.Show the result in table 8~10.
A: becoming argillaceous, and the surface BMC is dry, not condensation product attachment, and BMC most assembles well.
B: slightly soft, but become argillaceous, the surface BMC is dry, not condensation product attachment, and BMC assembles well.
The surface C:BMC is dry, is attached with condensation product, the aggregation of BMC is poor.
(production of formed body)
It is respectively 150mm × 60mm × 4mm molding in cavity dimension for BMC obtained in embodiment and comparative example It is put into the BMC of 70g in template, carries out compression forming in 5 minutes under conditions of 120 DEG C of temperature, clamping pressure 6MPa and is fabricated to Type body.
The case where cracking, remove at the time of molding, being capable of forming desired formed body is evaluated as A, will at The case where cracking, remove when type, can not forming desired formed body is evaluated as B.Show the result in table 8~10.
(ocular estimate of formed body)
It for obtained formed body, visually observes its appearance and evaluates, evaluate whether there is part and appear as white Position.Show the result in table 8~10.
A: there is no the positions for partially appearing as white
B: there is the position that part appears as white
(evaluation when formed body scratches)
The surface of obtained formed body is scratched using the stone that Mohs' hardness is 7, visually observes and evaluation is scraped as follows Part after drawing.Evaluation result is shown in table 8~10.
A: the part after scratch does not bleach
B: the part after scratch bleaches, hence it is evident that
C: the part after scratch becomes white mark, more obvious than b
[table 8]
[table 9]
[table 10]
According to table 8~10, in embodiment, the BMC that can be assembled well.In addition, if using in embodiment Obtained BMC can then make formed body.Especially by using embodiment 1-2~1-5, embodiment 3-1~3-2, reality Apply BMC obtained in a 4-1~4-2, the surface of the formed body formed using the BMC will not generate part appear as it is white The position of color is capable of forming the formed body with particularly good appearance.If using embodiment 1-2~1-5, embodiment BMC obtained in 3-2, embodiment 4-1~4-2, even if the part after scratch is not yet further to formed body surface scratches It can bleach, the situation that damage location appears as white can be efficiently reduced.
Industrial availability
The solidification compound that can assemble well of the invention can be suitable for being formed appearance well and even if damage Also can efficiently reduce damage location appear as white situation formed body, can be suitable for kitchen basin, table top or The various uses such as washbowl.

Claims (18)

1. a kind of solidification compound contains ingredient below:
Ingredient A: the monomer containing 1 or more carbon-to-carbon unsaturated bond,
Ingredient B: carbon black, and
Ingredient C: curing agent；
Relative to the ingredient A of 100 mass parts, the ingredient B is contained with 5 mass parts~45 mass parts range.
2. solidification compound according to claim 1, wherein the ingredient A contains following compositions A1,
Ingredient A1: contain the monomer of 1 or more (methyl) acryloyl group.
3. solidification compound according to claim 2, wherein the ingredient A1 contains following compositions A1-1 and A1-2 At least one of,
Ingredient A1-1: the monomer with 1 (methyl) acryloyl group,
Ingredient A1-2: the monomer with 2 or more (methyl) acryloyl groups.
4. solidification compound according to claim 3, wherein relative to the ingredient A1 of 100 mass parts, with 40 matter Amount part~100 mass parts range contains the ingredient A1-2.
5. solidification compound according to claim 1, wherein further contain following compositions A ',
Ingredient A ': the polymer with the Component units from the ingredient A.
6. solidification compound according to claim 5, wherein the ingredient A ' is with from (methyl) propylene The polymer of the Component units of the monomer of acyl group.
7. solidification compound according to claim 5, wherein the ingredient A ' has cross-linked structure.
8. solidification compound according to claim 5, wherein the ingredient A ' is with 1 μm~100 μm of average grain diameter Particle shape.
9. solidification compound according to claim 1, wherein further contain following compositions B ',
Ingredient B ': calcining at least one of silica sand and graphite.
10. solidification compound according to claim 9, wherein the ingredient B ' is calcining silica sand,
Relative to the ingredient A of 100 mass parts, which is contained with 10 mass parts~300 mass parts range.
11. solidification compound according to claim 9, wherein the ingredient B ' is graphite,
Relative to the ingredient A of 100 mass parts, which is contained with 0.5 mass parts~10 mass parts range.
12. solidification compound according to claim 1, wherein further contain inorganic filler.
13. solidification compound according to claim 12, wherein inorganic filler is selected from silica filler, glass filler At least one of with glass fibre.
14. solidification compound according to claim 1, wherein further contain lower shrinkage agent.
15. a kind of formed body is obtained from solidifying solidification compound described in any one of claim 1~14.
16. formed body according to claim 15, wherein formed body is kitchen basin, table top or washbowl.
17. a kind of manufacturing method of formed body, including prepare the process a of solidification compound and solidify solidification compound and The process b of formed body is formed,
Wherein, the solidification compound at least contains ingredient below:
Ingredient A: the monomer containing 1 or more carbon-to-carbon unsaturated bond,
Ingredient B: carbon black, and
Ingredient C: curing agent；
Also, relative to the ingredient A of 100 mass parts, the ingredient B is contained with 5 mass parts~45 mass parts range.
18. the manufacturing method of formed body according to claim 17, wherein process b includes under 100 DEG C or more of heating By 1 minute~50 minutes processes of solidification compound compression forming.
CN201810802148.5A 2017-07-21 2018-07-20 Solidification compound, formed body and its manufacturing method Pending CN109280309A (en)

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JP2017-142300 2017-07-21
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JP2018136015A JP2019023287A (en) 2017-07-21 2018-07-19 Curable composition, molding, and method for producing the same

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5381589A (en) * 1976-12-27 1978-07-19 Mitsubishi Rayon Co Ltd Manufacturing of marble-like cured product
JPH04300943A (en) * 1991-03-28 1992-10-23 Kuraray Co Ltd Acrylic artificial marble having pitch-black color and its production
US5596036A (en) * 1991-06-14 1997-01-21 Sandoz Ltd. Hardenable acrylic monomer compositions
CN1299400A (en) * 1998-04-09 2001-06-13 普鲁斯－斯托弗股份公司 Composite compositions of co-structured or co-adsorbed organic or mineral pigments or fillers and their uses
EP2112182A1 (en) * 2008-04-25 2009-10-28 FUJIFILM Corporation Polymerizable composition, light-shielding color filter, black curable composition, light-shielding color filter for solid-state image pickup device and method of producing the same, and solid-state image pickup device
CN102245645A (en) * 2008-12-16 2011-11-16 昭和电工株式会社 Hardening composition and hardened product of same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5381589A (en) * 1976-12-27 1978-07-19 Mitsubishi Rayon Co Ltd Manufacturing of marble-like cured product
JPH04300943A (en) * 1991-03-28 1992-10-23 Kuraray Co Ltd Acrylic artificial marble having pitch-black color and its production
US5596036A (en) * 1991-06-14 1997-01-21 Sandoz Ltd. Hardenable acrylic monomer compositions
CN1299400A (en) * 1998-04-09 2001-06-13 普鲁斯－斯托弗股份公司 Composite compositions of co-structured or co-adsorbed organic or mineral pigments or fillers and their uses
EP2112182A1 (en) * 2008-04-25 2009-10-28 FUJIFILM Corporation Polymerizable composition, light-shielding color filter, black curable composition, light-shielding color filter for solid-state image pickup device and method of producing the same, and solid-state image pickup device
CN102245645A (en) * 2008-12-16 2011-11-16 昭和电工株式会社 Hardening composition and hardened product of same

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