CN103534284A - Methacrylic resin composition and molded product thereof - Google Patents
Methacrylic resin composition and molded product thereof Download PDFInfo
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- CN103534284A CN103534284A CN201280023692.0A CN201280023692A CN103534284A CN 103534284 A CN103534284 A CN 103534284A CN 201280023692 A CN201280023692 A CN 201280023692A CN 103534284 A CN103534284 A CN 103534284A
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- methacrylic acid
- resin composition
- based resin
- methacrylic
- ester
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
Abstract
The purpose of the present invention is to provide a methacrylic resin composition whereby the occurrence of shrinkage upon curing can be reduced while keeping heat resistance and transparency. This methacrylic resin composition comprises a methacrylic acid ester compound comprising at least one cyclic methacrylic acid ester, a polyfunctional unsaturated ester compound, and a radical polymerization initiator having a 10-hour half-life temperature of 50-100 C.
Description
Technical field
The present invention relates to methacrylic acid based resin composition and formed body thereof, particularly can the suitable surrogate that is used as the sheet glass of vehicle use, window-glass for building, the cover of solar panel etc.
Background technology
Methacrylate compound is brought into play the characteristics such as the transparency, weathering resistance, surface hardness and is used as various formed materials (for example, with reference to patent documentation 1).Yet the cure shrinkage of methacrylate compound is large, be difficult to moulding.That is, the vinyl being present in molecular chain of methacrylate compound reacts.Intermolecular distance (0.3～0.6nm) between the known vinyl now existing before reaction becomes singly-bound (0.14nm) through reaction, and therefore reaction causes shrinking.
For reducing this cure shrinkage, carried out various research in recent years.Conventionally known to adding little material or the low material of second-order transition temperature of acrylic equivalent as chain alkyl (methyl) acrylate, can reduce cure shrinkage.Yet although these methods can reduce cure shrinkage, thermotolerance reduces.So, as the method that maintains thermotolerance and minimizing cure shrinkage, add the cure shrinkage inorganic particulate less than methacrylic ester.In this case, by adding inorganic particulate, although can significantly reduce cure shrinkage, the transparency significantly reduces.
Prior art document
Patent documentation
Patent documentation 1: No. WO98/55885, International Publication
Summary of the invention
The technical problem that invention will solve
The present invention completes in view of above-mentioned aspect, and its object is, providing a kind of can maintain thermotolerance and reduce the methacrylic acid based resin composition of cure shrinkage and the formed body that has utilized said composition transparent in the situation that.
Means for technical solution problem
Methacrylic acid based resin composition of the present invention is characterised in that, it is that to contain the methacrylate compound that at least comprises a kind of ring-type methacrylic ester, multifunctional unsaturated ester compound and 10 hours half life temperatures be that the radical polymerization initiator of 50～100 ℃ forms.
In methacrylic acid based resin composition of the present invention, the ratio of above-mentioned ring-type methacrylic ester is preferably 5～40 quality % of above-mentioned methacrylate compound.
In methacrylic acid based resin composition of the present invention, preferably by making acrylic resin or methacrylic resin dissolve to contain.
In methacrylic acid based resin composition of the present invention, preferably contain the acrylic acid derivative with hindered piperidine skeleton or methacrylic acid derivative that the total amount with respect to above-mentioned methacrylate compound is 0.1～10%.
In methacrylic acid based resin composition of the present invention, preferably contain and in the skeleton that the total amount with respect to above-mentioned methacrylate compound is 0.1～10%, there is acrylic acid derivative or the methacrylic acid derivative that absorbs ultraviolet functional group.
Formed body of the present invention is characterised in that, it forms the moulding of above-mentioned methacrylic acid based resin composition.
In formed body of the present invention, preferably contain the above-mentioned ring-type methacrylic ester of 5～40 quality %.
Invention effect
Methacrylic acid based resin composition of the present invention and formed body thereof can maintain thermotolerance and reduce cure shrinkage transparent in the situation that.
Embodiment
Below, to describing for implementing mode of the present invention.
It is the radical polymerization initiator of 50 ℃～100 ℃ that methacrylic acid based resin composition in the present invention contains the methacrylate compound that at least contains a kind of ring-type methacrylic ester, multifunctional unsaturated ester compound and 10 hours half life temperatures.In addition, can also contain as required acrylic resin.
As above-mentioned ring-type methacrylic ester, such as using cyclohexyl methacrylate, methacrylic acid benzene oxygen ester, methacrylic acid 4-tertiary butyl cyclohexyl, phenoxy group polyethylene glycol methacrylate-styrene polymer, methacrylic acid dicyclopentenyl oxygen base ethyl ester, methacrylic acid three ring esters in the last of the ten Heavenly stems, methacrylic acid phenoxy ethyl, benzyl methacrylate, methacrylic acid diamantane ester, trimethylene oxide methacrylic ester, gamma-butyrolactone methacrylic ester, isobornyl methacrylate, methacrylic acid two cyclopentenes esters, tetrahydrofurfuryl methacrylate etc.They can be used, or two or more may be used.
The content of this ring-type methacrylic ester is particularly preferably 5～40 quality % with respect to the total amount of methacrylate compound.When the content of ring-type methacrylic ester is within the scope of this, the cure shrinkage in the time of can reducing the moulding of methacrylic acid based resin composition.
As the spendable methacrylic ester except above-mentioned ring-type methacrylic ester, such as using methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, 2-Ethylhexyl Methacrylate, lauryl methacrylate, propyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester etc.They can be used, or two or more may be used.
As above-mentioned multifunctional unsaturated ester compound, for example can use Vinylstyrene ethylene glycol dimethacrylate, Vinylstyrene glycol diacrylate, ethylene glycol dimethacrylate, EDIA, Diethylene Glycol dimethacrylate, diethylene glycol diacrylate, TEGDMA, triethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol acrylate, 1, 3-butylene glycol dimethacrylate, 1, ammediol dimethacrylate, 1, 4-butylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, the difunctionality unsaturated ester such as neopentylglycol dimethacrylate, the trifunctional unsaturated ester such as trimethylolethane trimethacrylate methacrylic ester, trimethylolethane trimethacrylate acrylate, trimethylolpropane trimethacrylate, Viscoat 295, tetramethylol methane trimethacrylate, tetramethylol methane triacrylate, the four sense unsaturated ester such as tetramethylol methane tetramethyl-acrylate, tetramethylol methane tetraacrylate, dipropylene glycol dimethacrylate, propylene glycol diacrylate.They can be used, or two or more may be used.
As above-mentioned 10 hours half life temperatures, be the radical polymerization initiator of 50～100 ℃, can use diacyl peroxide class, ketal peroxide class, alkyl super-acid ester class, peroxocarbonate class.For example can enumerate two (3,3,5-trimethyl acetyl base) superoxide, two bay acyl peroxides, dibenzoyl superoxide, 1,1-bis-(tert-butyl hydroperoxide) hexanaphthene, 2,2-bis-(t-amyl peroxy) butane, 2,2-bis-(4,4-, bis-uncles (butyl peroxy) cyclohexyl) propane, the new enanthic acid tert-butyl ester of peroxidation, talkyl peropivalate, the peroxidation trimethylacetic acid tert-butyl ester, peroxidation-2 ethyl hexanoic acid 1,1,3,3-tetramethyl-butyl ester, disuccinic acid superoxide, 2,5-dimethyl-2,5-bis-(peroxidation of 2-ethyl hexyl acyl group) hexane, the tertiary own ester of peroxidation-2 ethyl hexanoic acid, two (4-methyl benzoyl) superoxide, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, peroxidation six hydrogen terephthalic acid di tert butyl carbonates, peroxidation 3,3,5-tri-methyl hexanoic acid tert-pentyl ester, peroxidation sec.-propyl carbonic acid tert-pentyl ester, tert-butylperoxy isopropyl carbonate, peroxidation-2-ethylhexyl carbonic acid tert-butyl ester, 1,6-bis-(tert-butyl hydroperoxide carbonyl acyloxy) hexane, diethyl peroxide tert.-butyl acetate, 1,1-bis-(tert-butyl hydroperoxide)-2-methylcyclohexane, 1,1-bis-(tertiary hexyl peroxidation)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(tertiary hexyl peroxidation) hexanaphthene, the tertiary own ester of peroxidation sec.-propyl carbonic acid, the toxilic acid peroxidation tert-butyl ester, peroxidation-3,3, the 5-tri-methyl hexanoic acid tert-butyl ester, the peroxidation lauric acid tert-butyl ester, the tertiary own ester of benzoyl peroxide formic acid, 2,5-dimethyl-2, the known organo-peroxides such as 5-bis-(benzoyl peroxidation) hexane, they can be used, or two or more may be used.It should be noted that, within 10 hours, half life temperature is known index, refers to that under hot effect polymerization starter decomposes, and through the concentration of 10 hours post polymerization initiators, reduces to half initial required temperature.
When radical polymerization initiator within 10 hours, half life temperature is in above-mentioned scope time, can suppress to solidify deficiency, foaming etc., therefore preferred.
In the present invention, can be as required by making (methyl) acrylic resin dissolve to coordinate.It should be noted that, " (methyl) acrylic " refers to methacrylic acid group or acrylic.By cooperation, be somebody's turn to do (methyl) acrylic resin, can expect viscosity adjustment, improve formability.As (methyl) acrylic resin using in the present invention, such as using homopolymer or the multipolymer being obtained by alkyl methacrylates such as the alkyl acrylates such as methacrylic ester, ethyl propylene acid esters, butylacrylic acid ester and/or methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate.In addition, also can use the multipolymer of the monomer that these monomers and other can copolymerization.Particularly from the viewpoint of reactivity, weathering resistance, transparent, preferred polymethylmethacrylate (PMMA).In addition, 10～30 quality % that particularly preferably acrylic resin is methacrylate compound.This acrylic resin can be by solution polymerization, emulsion polymerization, be suspended the common polymerization processs such as polymerization manufactures, and its manufacture method is not particularly limited.
When the formed body being formed by methacrylic acid based resin composition in the past irradiates the light time, sometimes pass in time the transparency and can reduce.Consider this be due to: the Resorcinol containing as impurity in the monomer of methacrylic acid based resin composition is transformed into benzoquinones under the effect of the free radical being generated by ultraviolet ray.
So, in the present invention, can coordinate as required acrylic acid derivative or the methacrylic acid derivative with hindered piperidine skeleton.By coordinating this acrylic acid derivative with hindered piperidine skeleton or methacrylic acid derivative, can expect that photostabilization improves.This is because hindered piperidine skeleton has seizure by the free radical of light (particularly ultraviolet ray) generation and by the effect of its deactivation.As the acrylic acid derivative with hindered piperidine skeleton or the methacrylic acid derivative that use in the present invention, can enumerate methacrylic acid 1,2,2,6,6-pentamethyl--4-piperidine ester (for example ADK STAB LA-82 of Asahi Denka Co., Ltd.'s system), methacrylic acid 2,2,6,6-tetramethyl--4-piperidine ester (such as the ADK STAB LA-87 of Asahi Denka Co., Ltd.'s system) etc.
This acrylic acid derivative or the methacrylic acid derivative with hindered piperidine skeleton is preferably the content of 0.1～10 quality % with respect to the total amount of methacrylate compound, is particularly preferably the containing ratio of 1～3 quality %.When thering is the acrylic acid derivative of hindered piperidine skeleton or the content of methacrylic acid derivative and be 0.1～10 quality %, can improve weathering resistance in the situation that do not affect the formability of methacrylic acid based resin composition.
In addition, in the present invention, can coordinate as required acrylic acid derivative or the methacrylic acid derivative in skeleton with the ultraviolet functional group of absorption.By coordinating in this skeleton, there is acrylic acid derivative or the methacrylic acid derivative that absorbs ultraviolet functional group, can expect that weathering resistance improves.This be because, when making the polymkeric substance of methacrylic ester have to absorb ultraviolet functional group by polymerization, can be in the situation that maintain the characteristic of acrylic resin, in resin surface or the absorbed inside ultraviolet ray of formed body.Namely when thering is ultraviolet absorption ability, can be in the resin surface of formed body or the inner generation that suppresses the free radical that be caused by ultraviolet ray.As thering is acrylic acid derivative or the methacrylic acid derivative that absorbs ultraviolet functional group in the skeleton using in the present invention, can enumerate 1-(2-benzotriazole)-2-hydroxyl-5-(2-methacryloxyethyl) benzene or its similar compound.
Acrylic acid derivative or the methacrylic acid derivative in this skeleton with the ultraviolet functional group of absorption are preferably the content of 0.1～10 quality % with respect to the total amount of methacrylate compound, are particularly preferably the containing ratio of 1～3 quality %.In skeleton, have when absorbing the acrylic acid derivative of ultraviolet functional group or the content of methacrylic acid derivative and being 0.1～10 quality %, can be in the situation that do not affect the transparent weathering resistance that improves of methacrylic acid based resin composition.
Can not affect transparent degree, to contain titanium oxide, zinc oxide, cerium oxide etc. inorganic be screening uv-ray agent in above-mentioned methacrylic acid based resin composition, also can contain in addition other photostabilizer, antioxidant, thermo-stabilizer, antistatic agent, invisible heat tamper, invisible heat absorption agent, fire retardant, lubricant, pigment, filler etc.
And methacrylic acid based resin composition of the present invention can be prepared by the radical polymerization initiator of 50 ℃～100 ℃ by coordinating methacrylate compound, multifunctional unsaturated ester compound and 10 hours half life temperatures.At this, mixing ratio about each composition, with respect to 100 mass parts methacrylate compound, multifunctional unsaturated ester compound can be 0.5～20 mass parts, and 10 hours half life temperatures are that the radical polymerization initiator of 50 ℃～100 ℃ can be 0.1～5 mass parts.When coordinating each composition with this mixing ratio, can obtain thermotolerance, the transparency is excellent and has reduced the methacrylic acid based resin composition of cure shrinkage.
Formed body of the present invention can, by above-mentioned methacrylic acid based resin composition is injected in the mould bases such as mould, resin mold, glass molds, solidifies it and obtain under pressurization or normal pressure, in certain specific temperature range.In addition, also methacrylic acid based resin composition can be coated on and on above-mentioned mould bases, obtain membranaceous formed body.For an one example, describe, can be injected in mould containing the above-mentioned methacrylic acid based resin composition that at least contains the methacrylate compound of a kind of ring-type methacrylic ester, above-mentioned multifunctional unsaturated ester compound and above-mentioned radical polymerization initiator, it is heating and curing, obtains formed body.Now, the temperature that is preferably heating and curing be 50 ℃ above and lower than 100 ℃, particularly preferably 60 ℃ above and lower than the scope of 90 ℃.When the temperature that is heating and curing is during more than 50 ℃ and lower than 100 ℃, can obtain thermotolerance, transparent excellence and the few formed body of cure shrinkage.
And as mentioned above by making methacrylic acid based resin composition contain ring-type methacrylic ester, in thermotolerance and transparency excellence, cure shrinkage is reduced.This methacrylic acid resin moldings is so long as effectively utilize the purposes of the transparency, weathering resistance, can be for any purposes, and can be film or the sheet of 30 μ m～1mm left and right.Particularly because cure shrinkage is few, therefore when will be by the formed body moulding of thick thing (thickness is 1～10mm), can above-mentioned preferred use methacrylic acid based resin composition.
When by above-mentioned methacrylic acid based resin composition moulding, multifunctional unsaturated ester compound becomes cross-linking set, can obtain the formed body with three-dimensional crosslinking structure.Because this formed body has three-dimensional crosslinking structure, the formed body therefore forming with methacrylic acid based resin composition by not having three-dimensional crosslinking structure is compared, excellent heat resistance.In addition, also excellent as the transparency of methacrylic ester feature.In addition, by use, suppress the ring-type methacrylic ester of cure shrinkage, can also be in the three-dimensional crosslinking structure forming by multifunctional unsaturated ester compound formation, acquisition thermotolerance, the formed body that the transparency is excellent, cure shrinkage is few.
Embodiment
Below, by embodiment, specifically describe the present invention, but the present invention is not limited only to these embodiment.
(embodiment 1)
In methyl methacrylate ［ Chemical formula 1 ］ 90 mass parts, mix as isobornyl methacrylate ［ Chemical formula 2 ］ 10 mass parts of ring-type methacrylic ester, as trimethylolpropane trimethacrylate ［ chemical formula 3 ］ 1 mass parts of multifunctional unsaturated ester compound with as two (3 of radical polymerization initiator; 5; 5-trimethyl acetyl base) superoxide 0.3 mass parts, obtains methacrylic acid based resin composition.Wherein, radical polymerization initiator has been used the Trigonox36-C75 of chemical drug Akzo Co., Ltd..Then, the methacrylic acid based resin composition being prepared into is like this poured in mould, it is solidified under the condition of 75 ℃, 1 hour, obtain formed body.
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
(embodiment 2,6,7)
The ratio that coordinates that changes methyl methacrylate and ring-type methacrylic ester, in addition, carries out moulding similarly to Example 1.
(embodiment 5, comparative example 3)
Change the kind of radical polymerization initiator, in addition, carry out similarly to Example 1 moulding.
(embodiment 3)
In methyl methacrylate ［ Chemical formula 1 ］ 75 mass parts, mix isobornyl methacrylate ［ Chemical formula 2 ］ 10 mass parts as ring-type methacrylic ester, polymethylmethacrylate 15 mass parts, as trimethylolpropane trimethacrylate ［ chemical formula 3 ］ 1 mass parts of multifunctional unsaturated ester compound with as two (3 of radical polymerization initiator; 5; 5-trimethyl acetyl base) superoxide 0.3 mass parts, obtains methacrylic acid based resin composition.Wherein, radical polymerization initiator has been used the Trigonox36-C75 of chemical drug Akzo Co., Ltd..Then, the methacrylic acid based resin composition being prepared into is like this poured in mould, it is solidified under the condition of 75 ℃, 1 hour, obtain formed body.
(embodiment 4)
The ratio that coordinates that changes methyl methacrylate and polymethylmethacrylate, in addition, carries out moulding similarly to Example 3.
(embodiment 8)
In the isobornyl methacrylate as ring-type methacrylic ester ［ Chemical formula 2 ］ 100 mass parts, mix as trimethylolpropane trimethacrylate ［ chemical formula 3 ］ 1 mass parts of multifunctional unsaturated ester compound with as two (3 of radical polymerization initiator; 5; 5-trimethyl acetyl base) superoxide 0.3 mass parts, obtains methacrylic acid based resin composition.Wherein, radical polymerization initiator has been used the Trigonox36-C75 of chemical drug Akzo Co., Ltd..Then, the methacrylic acid based resin composition being prepared into is like this poured in mould, it is solidified under the condition of 75 ℃, 1 hour, obtain formed body.
(embodiment 9)
In methyl methacrylate ［ Chemical formula 1 ］ 90 mass parts, mix isobornyl methacrylate ［ Chemical formula 2 ］ 10 mass parts as ring-type methacrylic ester, as thering is the acrylic acid derivative of hindered piperidine skeleton or the methacrylic acid of methacrylic acid derivative 1, 2, 2, 6, 6-pentamethyl--4-piperidine ester ［ chemical formula 4 ］ 1 mass parts, trimethylolpropane trimethacrylate ［ chemical formula 3 ］ 1 mass parts as multifunctional unsaturated ester compound, with as two (3 of radical polymerization initiator, 5, 5-trimethyl acetyl base) superoxide 0.3 mass parts, obtain methacrylic acid based resin composition.Wherein, radical polymerization initiator is used the Trigonox36-C75 of chemical drug Akzo Co., Ltd., has the acrylic acid derivative of hindered piperidine skeleton or the ADK STAB LA-82 that methacrylic acid derivative has been used Asahi Denka Co., Ltd.'s system.Then, the methacrylic acid based resin composition being prepared into is like this poured in mould, it is solidified under the condition of 75 ℃, 1 hour, obtain formed body.
[chemical formula 4]
(embodiment 10,11,16)
Change methyl methacrylate with have hindered piperidine skeleton methacrylic acid derivative coordinate ratio, in addition, carry out similarly to Example 9 moulding.
(embodiment 12)
In methyl methacrylate ［ Chemical formula 1 ］ 90 mass parts, mix isobornyl methacrylate ［ Chemical formula 2 ］ 10 mass parts as ring-type methacrylic ester, as thering is the acrylic acid derivative of ultraviolet functional group of absorption or the 1-(2-benzotriazole of methacrylic acid derivative in skeleton)-2-hydroxyl-5-(2-methacryloxyethyl) benzene ［ chemical formula 5 ］ 1 mass parts, trimethylolpropane trimethacrylate ［ chemical formula 3 ］ 1 mass parts as multifunctional unsaturated ester compound, with as two (3 of radical polymerization initiator, 5, 5-trimethyl acetyl base) superoxide 0.3 mass parts, obtain methacrylic acid based resin composition.Wherein, radical polymerization initiator has been used the Trigonox36-C75 of chemical drug Akzo Co., Ltd., has and absorb the acrylic acid derivative of ultraviolet functional group or the RUVA-93 that methacrylic acid derivative is used Otsuka Chemical Co., Ltd system in skeleton.Then, the methacrylic acid based resin composition being prepared into is like this poured in mould, it is solidified under the condition of 75 ℃, 1 hour, obtain formed body.
[chemical formula 5]
(embodiment 13,14,17)
Change methyl methacrylate with in skeleton, have the ultraviolet functional group of absorption methacrylic acid derivative coordinate ratio, in addition, carry out similarly to Example 12 moulding.
(embodiment 15)
In methyl methacrylate ［ Chemical formula 1 ］ 90 mass parts, mix isobornyl methacrylate ［ Chemical formula 2 ］ 10 mass parts as ring-type methacrylic ester, as thering is the acrylic acid derivative of hindered piperidine skeleton or the methacrylic acid of methacrylic acid derivative 1, 2, 2, 6, 6-pentamethyl--4-piperidine ester ［ chemical formula 4 ］ 1 mass parts, as thering is the acrylic acid derivative of ultraviolet functional group of absorption or the 1-(2-benzotriazole of methacrylic acid derivative in skeleton)-2-hydroxyl-5-(2-methacryloxyethyl) benzene ［ chemical formula 5 ］ 1 mass parts, trimethylolpropane trimethacrylate ［ chemical formula 3 ］ 1 mass parts as multifunctional unsaturated ester compound, with as two (3 of radical polymerization initiator, 5, 5-trimethyl acetyl base) superoxide 0.3 mass parts, obtain methacrylic acid based resin composition.Wherein, radical polymerization initiator has been used the Trigonox36-C75 of chemical drug Akzo Co., Ltd., there is the acrylic acid derivative of hindered piperidine skeleton or the ADK STAB LA-82 that methacrylic acid derivative has been used Asahi Denka Co., Ltd.'s system, in skeleton, have and absorb the acrylic acid derivative of ultraviolet functional group or the RUVA-93 that methacrylic acid derivative is used Otsuka Chemical Co., Ltd system.Then, the methacrylic acid based resin composition being prepared into is like this poured in mould, it is solidified under the condition of 75 ℃, 1 hour, obtain formed body.
(comparative example 1)
In methyl methacrylate ［ Chemical formula 1 ］ 100 mass parts, mix as trimethylolpropane trimethacrylate ［ chemical formula 3 ］ 1 mass parts of multifunctional unsaturated ester compound with as two (3 of radical polymerization initiator; 5; 5-trimethyl acetyl base) superoxide 0.3 mass parts, obtains methacrylic acid based resin composition.Wherein, radical polymerization initiator is used the Trigonox36-C75 of chemical drug Akzo Co., Ltd..Then, the methacrylic acid based resin composition being prepared into is like this poured in mould, it is solidified under the condition of 75 ℃, 1 hour, obtain formed body.
(comparative example 2)
In methyl methacrylate ［ Chemical formula 1 ］ 90 mass parts, mix polymethylmethacrylate 10 mass parts, as trimethylolpropane trimethacrylate ［ chemical formula 3 ］ 1 mass parts of multifunctional unsaturated ester compound with as two (3 of radical polymerization initiator; 5; 5-trimethyl acetyl base) superoxide 0.3 mass parts, obtains methacrylic acid based resin composition.Wherein, radical polymerization initiator is used the Trigonox36-C75 of chemical drug Akzo Co., Ltd..Then, the methacrylic acid based resin composition being prepared into is like this poured in mould, it is solidified under the condition of 75 ℃, 1 hour, obtain formed body.
< performance evaluation >
The outward appearance of the formed body being as above made into, the transparency, thermotolerance and cure shrinkage are evaluated.
(1) outward appearance
The outward appearance of formed body is by visual observation, there is no be designated as " zero " of cracking, foaming, albefaction, has be designated as " * " of cracking, foaming, albefaction.
(2) transparency
The products formed that the transparent used thickness of the formed body obtaining is 3mm be take JIS K7105 and is carried out as benchmark.
(3) thermotolerance
The thermotolerance of the products formed obtaining is utilized second-order transition temperature evaluation.The mensuration of second-order transition temperature be take JIS K7121 and is carried out as benchmark.
(4) cure shrinkage
The cure shrinkage of the products formed obtaining be take JIS K6901 as benchmark mensuration.
(5) weathering resistance
Atmospheric exposure test is used the DPWL-5R of Suga test system to carry out.As test conditions, based on JIS A1415 and JIS K7350-3, carry out.After 6 samples are placed in two plate weatherometers (dual panel weather meter), setting black side plate temperature is that 63 ℃ (during irradiations), radiation illumination are 30W/m
2(300～400nm), irradiates 4 hours, and to turn off the light, (dewfall) testing campaign of 4 hours is carried out 200 hours.As evaluation method, at resin back side configuration blank, with colour-difference meter, measure, by the colour-change before and after the test of Δ E value representation.
Table 1
As shown in Table 1, embodiment 1～8 and comparative example 1,2 contrasts, the transparency is equal, excellent heat resistance, cure shrinkage is suppressed.In embodiment 9～15, weathering resistance is more excellent.Therefore,, when coordinating ring-type methacrylic ester in methacrylic acid based resin composition, can maintain thermotolerance and reduce cure shrinkage transparent in the situation that.In addition,, when having when thering are any or two kinds that absorb in the ultraviolet person of functional group in hindered piperidine skeleton person and skeleton and being coupled in above-mentioned methacrylic acid based resin composition, can improve the weathering resistance of formed body.In addition, when as embodiment 16,17 in methacrylic acid based resin composition a large amount of cooperation while thering is the methacrylic acid derivative that absorbs ultraviolet functional group in the methacrylic acid derivative, skeleton with hindered piperidine skeleton, there is the thermotolerance of formed body or the tendency that the transparency reduces.
Claims (7)
1. a methacrylic acid based resin composition, it is characterized in that, it is that to contain the methacrylate compound that at least comprises a kind of ring-type methacrylic ester, multifunctional unsaturated ester compound and 10 hours half life temperatures be that the radical polymerization initiator of 50～100 ℃ forms.
2. methacrylic acid based resin composition according to claim 1, is characterized in that, the ratio of ring-type methacrylic ester is 5～40 quality % with respect to the total amount of methacrylate compound.
3. methacrylic acid based resin composition according to claim 1 and 2, is characterized in that, by making acrylic resin or methacrylic resin dissolve to contain.
4. according to the methacrylic acid based resin composition described in any one in claim 1～3, it is characterized in that, contain the acrylic acid derivative with hindered piperidine skeleton or methacrylic acid derivative that the total amount with respect to described methacrylate compound is 0.1～10%.
5. according to the methacrylic acid based resin composition described in any one in claim 1～4, it is characterized in that, contain and in the skeleton that the total amount with respect to described methacrylate compound is 0.1～10%, there is acrylic acid derivative or the methacrylic acid derivative that absorbs ultraviolet functional group.
6. a formed body, is characterized in that, it is that the methacrylic acid based resin composition moulding described in any one in claim 1～5 is formed.
7. formed body according to claim 6, is characterized in that, it is that the ring-type methacrylic ester that contains 5～40 quality % forms.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011114867 | 2011-05-23 | ||
| JP2011-114867 | 2011-05-23 | ||
| JP2011228992 | 2011-10-18 | ||
| JP2011-228992 | 2011-10-18 | ||
| PCT/JP2012/062714 WO2012161100A1 (en) | 2011-05-23 | 2012-05-17 | Methacrylic resin composition and molded product thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103534284A true CN103534284A (en) | 2014-01-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201280023692.0A Pending CN103534284A (en) | 2011-05-23 | 2012-05-17 | Methacrylic resin composition and molded product thereof |
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| Country | Link |
|---|---|
| JP (1) | JPWO2012161100A1 (en) |
| CN (1) | CN103534284A (en) |
| WO (1) | WO2012161100A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107856468A (en) * | 2017-11-30 | 2018-03-30 | 江阴市新城东天工专业设计工作室 | A kind of Ornamental Stone base and preparation method thereof |
| CN110494425A (en) * | 2017-03-29 | 2019-11-22 | 希普洛化成股份有限公司 | Benzotriazole derivatives compound and application thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI585144B (en) * | 2014-10-21 | 2017-06-01 | Mitsubishi Rayon Co | (Meth) acrylic resin composition and a resin molded product |
| JP2020105492A (en) * | 2018-12-26 | 2020-07-09 | 東洋インキＳｃホールディングス株式会社 | Ultraviolet-absorbing monomer, acrylic polymer, resin composition, and molding |
| CN113454132B (en) * | 2019-02-20 | 2023-05-09 | 东洋油墨Sc控股株式会社 | Ultraviolet-absorbing polymer, molding resin composition, and molded article |
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| JPS6183213A (en) * | 1984-09-29 | 1986-04-26 | Kyowa Gas Chem Ind Co Ltd | Disk base and its production |
| JP2564273B2 (en) * | 1986-04-01 | 1996-12-18 | 日立化成工業 株式会社 | Casting optical resin material |
| JPH02133415A (en) * | 1988-11-14 | 1990-05-22 | Hitachi Chem Co Ltd | Production of high refractive index plastic lens |
| JPH10130331A (en) * | 1996-10-28 | 1998-05-19 | Kureha Chem Ind Co Ltd | Lid material for solid-state image sensing element package made of plastic and its production |
| WO2000026698A1 (en) * | 1998-10-29 | 2000-05-11 | Allergan Sales, Inc. | Intraocular lenses made from polymeric compositions |
| JP2000264929A (en) * | 1999-03-17 | 2000-09-26 | Hitachi Chem Co Ltd | Optical copolymer, production of optical copolymer and optical part |
| JP2004156025A (en) * | 2002-10-17 | 2004-06-03 | Nippon Shokubai Co Ltd | Aqueous resin dispersion, aqueous resin composition and method for producing aqueous resin composition |
| JP2004224891A (en) * | 2003-01-22 | 2004-08-12 | Mitsubishi Rayon Co Ltd | Acrylic resin resin plate and method for producing the same |
| US20060155085A1 (en) * | 2003-06-09 | 2006-07-13 | Mitsui Chemicals, Inc. | Crosslinkable methacrylic resin composition and transparent member |
| EP2163566B1 (en) * | 2007-07-02 | 2013-09-18 | Idemitsu Kosan Co., Ltd. | Resin for optical component, raw material composition used for resin for optical component, and optical component |
-
2012
- 2012-05-17 CN CN201280023692.0A patent/CN103534284A/en active Pending
- 2012-05-17 JP JP2013516334A patent/JPWO2012161100A1/en active Pending
- 2012-05-17 WO PCT/JP2012/062714 patent/WO2012161100A1/en active Application Filing
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110494425A (en) * | 2017-03-29 | 2019-11-22 | 希普洛化成股份有限公司 | Benzotriazole derivatives compound and application thereof |
| CN110494425B (en) * | 2017-03-29 | 2022-08-16 | 希普洛化成股份有限公司 | Benzotriazole derivative compound and use thereof |
| CN107856468A (en) * | 2017-11-30 | 2018-03-30 | 江阴市新城东天工专业设计工作室 | A kind of Ornamental Stone base and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| JPWO2012161100A1 (en) | 2014-07-31 |
| WO2012161100A1 (en) | 2012-11-29 |
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