CN108884289A - The manufacturing method of (methyl) acrylic resin composition, resin-formed body, laminated resin body and (methyl) acrylic resin composition - Google Patents

The manufacturing method of (methyl) acrylic resin composition, resin-formed body, laminated resin body and (methyl) acrylic resin composition Download PDF

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Publication number
CN108884289A
CN108884289A CN201780018937.3A CN201780018937A CN108884289A CN 108884289 A CN108884289 A CN 108884289A CN 201780018937 A CN201780018937 A CN 201780018937A CN 108884289 A CN108884289 A CN 108884289A
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methyl
mass
resin composition
acrylic resin
resin
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中野正浩
石原丰
铃木正法
渡边博之
小泽觉
百濑扶实乃
小龟朗由
前中佑太
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

Abstract

The present invention provides (methyl) the acrylic resin composition with high flame retardant and the resin-formed body formed by above-mentioned (methyl) acrylic resin composition and the method for steadily manufacturing above-mentioned (methyl) acrylic resin composition.A kind of (methyl) acrylic resin composition, it contains (methyl) acrylic acid series polymeric compounds (P), phosphorus flame retardant (C) and amphiphilic compound (E), and (methyl) acrylic acid series polymeric compounds (P) include the repetitive unit of (methyl) acrylate (M) for the alicyclic type hydrocarbon for having aromatic hydrocarbyl or carbon atom number 3~20 from side chain.A kind of manufacturing method of (methyl) acrylic resin composition, it includes to include in advance in the raw material monomer of (methyl) acrylic resin composition and the composition of amphiphilic compound (E), addition phosphorus flame retardant (C) afterwards.

Description

(methyl) acrylic resin composition, resin-formed body, laminated resin body and (first Base) acrylic resin composition manufacturing method
Technical field
The present invention relates to (methyl) acrylic resin composition, resin-formed body, laminated resin body and above-mentioned (first Base) acrylic resin composition manufacturing method.
The application is existed based on March 24th, 2016 in the Patent 2016-059809 of Japanese publication, on March 31st, 2016 The Patent 2016-070516 of Japanese publication, on April 18th, 2016 are at Patent No. 2016-082736,2016 of Japanese publication April 19 Patent 2016-083664 in Japanese publication, the 2 days 2 months Patent 2017-017218 in Japanese publication in 2017 Number carry out CLAIM OF PRIORITY, its content is quoted to herein.
Background technique
There is the transparency, heat resistance and gasproof using methyl methacrylate as (methyl) acrylic resin of principal component Marquis's property is excellent, and mechanical strength, thermal property, molding processibility etc. achieve the performance of balance.Therefore, for illuminating material, The extensive purposes such as optical material, billboard, display, decoration element, building element, these purposes require anti-flammability and heat-resisting Property.
In general, if in order to (methyl) acrylic resin assign anti-flammability and add fire retardant, exist the transparency, Heat resistance reduces such problems.Therefore, carried out not damaging the transparency, heat resistance and assign the research of anti-flammability.
For example, proposing the anti-flammability methyl-prop comprising methacrylic resin and Firemaster 836 in patent document 1 Olefin(e) acid resin plate, the methacrylic resin contain the monomer that side chain has alicyclic type hydrocarbon, disclose in embodiment Two ring pentyl ester of methacrylic acid has the monomer of alicyclic type hydrocarbon as side chain.
In addition, being proposed in patent document 2 and patent document 3 comprising (methyl) acrylic acid series polymeric compounds and as resistance The anti-flammability methacrylic resin plate of the phosphorus series compound of agent is fired, (methyl) acrylic acid series polymeric compounds contain methyl-prop E pioic acid methyl ester and (methyl) isobornyl acrylate.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-046835 bulletin
Patent document 2：Japanese Unexamined Patent Publication 2015-086250 bulletin
Patent document 3：International Publication No. 2016/063898
Summary of the invention
Problems to be solved by the invention
However, in methacrylic resin plate documented by patent document 1, it is fire-retardant although obtaining heat resistance Property is insufficient.
In methacrylic resin plate documented by patent document 2, although anti-flammability improve, resin plate it is heat-resisting Property is insufficient.
Further, in methacrylic resin plate documented by patent document 3, although anti-flammability and heat-resisting can be had both Property, but in a certain specific manufacturing method, the phosphorus series compound used as fire retardant is sometimes in methacrylic resin It is aggregated in plate, therefore, cannot steadily manufacture the resin plate of excellent in flame retardance sometimes.
In such a case, it is desirable that do not damage the heat resistance of the feature as (methyl) acrylic resin, there is height The resin-formed body of anti-flammability, and (methyl) acrylic resin composition for manufacturing above-mentioned resin-formed body are stablized Ground manufactures the technology of above-mentioned (methyl) acrylic resin composition.
In addition, other than high flame retardant, being sometimes required that in automotive part, lighting supplies, various panels etc. on the way Impact resistance, marresistance.
The present invention is for the purpose of solving these problems.That is, the first object of the present invention is to provide with good heat-resisting Property, further there is (methyl) the acrylic resin composition of high flame retardant and include above-mentioned (methyl) acrylic resin The resin-formed body of composition.
The second object of the present invention is to provide the method for steadily manufacturing above-mentioned (methyl) acrylic resin composition.
The third object of the present invention is to provide with high flame retardant, further with the resin-formed body of high-impact And (methyl) acrylic resin composition for manufacturing above-mentioned resin-formed body.
The fourth object of the present invention is to provide with high flame retardant, further with the resin-formed body of high marresistance And (methyl) acrylic resin composition for manufacturing above-mentioned resin-formed body.
The method used for solving the problem
The above subject is solved by following inventions [1]~[32].
[1] a kind of (methyl) acrylic resin composition, is containing (methyl) acrylic acid series polymeric compounds (P), phosphorus system (methyl) acrylic resin composition of fire retardant (C) and amphiphilic compound (E),
Above-mentioned (methyl) acrylic resin composition is relative to above-mentioned 100 mass of (methyl) acrylic acid series polymeric compounds (P) Part, below the mass containing more than 5.0 mass parts of above-mentioned phosphorus flame retardant (C) 35.0, also,
Above-mentioned (methyl) acrylic resin composition is relative to above-mentioned 100 mass of (methyl) acrylic acid series polymeric compounds (P) Part, below the mass containing more than 0.01 mass parts of above-mentioned amphiphilic compound (E) 2.0, also, have in JIS K 6911- In 1995 fire resistance test A method within 3 minutes self-extinguishment anti-flammability.
[2] (methyl) acrylic resin composition according to [1], above-mentioned (methyl) acrylic acid series polymeric compounds (P) To include (methyl) acrylate (M) from side chain with the alicyclic type hydrocarbon of aromatic hydrocarbyl or carbon atom number 3~20 Repetitive unit polymer.
[3] a kind of (methyl) acrylic resin composition, is containing (methyl) acrylic acid series polymeric compounds (P), phosphorus system (methyl) acrylic resin composition of fire retardant (C) and amphipathic chemical combination (E),
Above-mentioned (methyl) acrylic acid series polymeric compounds (P) are comprising having aromatic hydrocarbyl or carbon atom number 3 from side chain The polymer of the repetitive unit of (methyl) acrylate (M) of~20 alicyclic type hydrocarbon,
The dispersion particle diameter of above-mentioned phosphorus flame retardant (C) in above-mentioned (methyl) acrylic resin composition be 0.8 μm with Under, also, there is the anti-flammability of the self-extinguishment within 3 minutes in the fire resistance test A method of JIS K 6911-1995.
[4] (methyl) acrylic resin composition according to [3], (methyl) acrylic resin composition are opposite In above-mentioned 100 mass parts of (methyl) acrylic acid series polymeric compounds (P), contain more than 5.0 mass parts of above-mentioned phosphorus flame retardant (C) 35.0 Below the mass below the mass with more than 0.01 mass parts of amphiphilic compound (E) 2.0.
[5] (methyl) acrylic resin composition according to any one of [1]~[4], above-mentioned amphipathic chemical combination Object (E) is anionic surfactant.
[6] (methyl) acrylic resin composition according to [5], above-mentioned anionic surfactant are alkyl The alkali metal salt of sulfosuccinic acid.
[7] (methyl) acrylic resin composition, the alkali metal salt of abovementioned alkyl sulfosuccinic acid according to [6] For dioctyl sodium sulphosuccinate.
[8] (methyl) acrylic resin composition according to any one of [1]~[5], above-mentioned phosphorus flame retardant (C) for selected from least one of phosphate containing halogen and phosphonate ester containing halogen, above-mentioned amphiphilic compound (E) is following chemistry Non-halogen phosphoric ester shown in formula (I).
(in formula (I), R indicates alkyl, naphthenic base, aryl, alkoxy, alkoxy carbonyl, alkyl carboxyl, alkylidene, sub- ring Alkyl, arlydene, aryl alkylene, polyoxyalkylenes, n are 1 or 2.)
[9] (methyl) acrylic resin composition according to [8], in above-mentioned formula (I), R is carbon atom number 2~24 Aliphatic alkyl.
[10] (methyl) acrylic resin composition according to any one of [1]~[9], above-mentioned (methyl) propylene Sour based polymer (P) is the gross mass relative to (methyl) acrylic acid series polymeric compounds (P), comprising deriving from methyl methacrylate 19.95 mass % of repetitive unit or more, 84.95 mass % hereinafter, and derive from above-mentioned (methyl) acrylate (M) repetition 3.6 mass % of unit or more, 80.0 mass % polymer below.
[11] (methyl) acrylic resin composition according to [10], above-mentioned (methyl) acrylic acid series polymeric compounds (P) comprising having the methacrylate (M1) of the alicyclic type hydrocarbon of aromatic hydrocarbyl or carbon atom number 3~20 from side chain Repetitive unit and have from side chain aromatic hydrocarbyl or carbon atom number 3~20 alicyclic type hydrocarbon acrylate (M2) Repetitive unit as derive from above-mentioned (methyl) acrylate (M) repetitive unit, also,
Comprising from above-mentioned methacrylate (M1) 10.0 mass % of repetitive unit or more, 79.5 mass % hereinafter, From 0.50 mass % of repetitive unit or more, the 20.0 mass % or less of above-mentioned acrylate (M2).
[12] (methyl) acrylic resin composition according to [10] or [11], above-mentioned (methyl) acrylic acid series are poly- Closing object (P) is the gross mass relative to (methyl) acrylic acid series polymeric compounds (P), comprising having 2 or more alkene in molecule Belong to 0.05 mass % of structural unit or more, the 0.40 mass % polymer below of the monomer (B) of unsaturated bond.
[13] (methyl) acrylic resin composition according to any one of [2]~[12], utilizes following measurements The half width at peak that method 1 measures the decomposition product of repetitive unit obtaining, from above-mentioned (methyl) acrylate (M) is 26 DEG C or less.
1 > of < measuring method
Using gas analysis measurement device (EGA-MS) occurs, by (methyl) acrylic resin composition 2mg in helium Under atmosphere (flow velocity 20ml/ minutes), with 10 DEG C/min of heating rate, the mass spectral analysis of the generation gas of decomposition product is carried out, is asked The half width at the peak of the decomposition product in temperature-chromatographic curve obtained out.
[14] (methyl) acrylic resin composition according to any one of [2]~[13], by following measurement sides The generation temperature of the decomposition product for the repetitive unit from above-mentioned (methyl) acrylate (M) that method 2 obtains and above-mentioned phosphorus system The generation temperature of the decomposition product of fire retardant (C) meets following formula (1).
|Tm-Tc|≤40 ···(1)
Tc：Generation temperature (the unit of phosphorus flame retardant (C) decomposition product：℃)
Tm：From the generation temperature (unit of the decomposition product of the repetitive unit of (methyl) acrylate (M)：℃)
2 > of < measuring method
Using gas analysis measurement device (EGA-MS) occurs, by (methyl) acrylic resin composition 2mg in helium Under atmosphere (flow velocity 20ml/ minutes), with 10 DEG C/min of heating rate, the mass spectral analysis of the generation gas of decomposition product is carried out, is found out The generation temperature of decomposition product in temperature-chromatographic curve of acquisition.
[15] (methyl) acrylic resin composition, the source obtained by said determination method 2 according to [14] In the generation temperature of the decomposition product of the repetitive unit of above-mentioned (methyl) acrylate (M) and from above-mentioned methyl methacrylate The generation temperature of the decomposition product of the repetitive unit of ester meets following formula (2).
100≤Ta-Tm ···(2)
Ta：From the generation temperature (unit of the decomposition product of the repetitive unit of methyl methacrylate：℃)
[16] (methyl) acrylic resin composition according to any one of [13]~[15], above-mentioned half width are 21 DEG C or less.
[17] (methyl) acrylic resin composition according to any one of [1]~[16] is utilized for using The MC (τ) and MP (τ) for the relaxation spectrum that solid NMR measurement device is observed by spin lock cross polarization method, by following formula (a) The value D being calculated1(%), the value D in spin lock time τ=30msec1(%) be 6.0 (%) below.
D1(%)=| MC (τ)-MP (τ) |/MC (τ) × 100 (a)
MC(τ)：The average value of the value of following (A) and (B)
When (A) by spin lock time τ sec13The carbon with carbonyl that 160ppm~180ppm of C nuclear ralaxation spectrum is observed When the area of corresponding spectrum is divided by 10 μ sec of spin lock time13160ppm~180ppm of C nuclear ralaxation spectrum is observed The carbon with carbonyl corresponding to spectrum the obtained value of area.
When (B) by spin lock time τ sec13The carbon with methylene that 30ppm~65ppm of C nuclear ralaxation spectrum is observed When the area of corresponding spectrum is divided by 10 μ sec of spin lock time13What 30ppm~65ppm of C nuclear ralaxation spectrum was observed The value that the area of spectrum corresponding to carbon with methylene obtains.
MP(τ)：When by spin lock time τ sec31- 40~40ppm of P nuclear ralaxation spectrum is observed and phosphorous flame-retardant When the area of spectrum corresponding to the phosphorus atoms of agent (C) is divided by 10 μ sec of spin lock time31- 40~40ppm institute of P core spectrum The value that the area of spectrum corresponding to the phosphorus atoms with phosphorus flame retardant (C) observed obtains.
[18] (methyl) acrylic resin composition according to [17], above-mentioned (methyl) acrylic resin combination In object, for the value D being calculated by above-mentioned formula (a)1(%), spin lock time τ=16msec, 20msec, 25msec, Each value D when 30msec1The average value D of (%)2(%) is 7.0% or less.
[19] (methyl) acrylic resin composition according to [17] or [18], above-mentioned phosphate and phosphonate ester Weight average molecular weight is 200 or more 500 or less.
[20] (methyl) acrylic resin composition according to any one of [1]~[19], above-mentioned (methyl) third Olefin(e) acid based resin composition is embedding comprising the multiplet acrylic acid series copolymer particle (D1) or acrylic acid series for being selected from following records At least one of section copolymer (D2) impact resistance modifier (D).
Multiplet acrylic acid series copolymer particle (D1)：With including the rubbery copolymer with cross-linked structure The multiplet acrylic acid series copolymer of the structure of hard resin layer (d1-2) is formed on the surface of elastomer particle (d1-1) Particle.
Acrylic block copolymer (D2)：With 10 mass % of methacrylate block (d2-1) or more, 60 matter Measure 90 mass % block copolymers below of % or less and acrylic ester polymerization block (d2-2) 40 mass % or more.
[21] (methyl) acrylic resin composition according to [20], above-mentioned (methyl) acrylic resin combination Object includes above-mentioned 2.0 mass parts of impact resistance modifier (D) relative to above-mentioned 100 mass parts of (methyl) acrylic acid series polymeric compounds (P) Above 50 below the mass.
[22] (methyl) acrylic resin composition according to [21], above-mentioned multiplet acrylic acid series copolymer In particle (D1), the rubbery copolymer for constituting above-mentioned elastomer particle (d1-1) includes using alkyl acrylate as principal component (co) polymer, above-mentioned hard resin layer (d1-2) include using methacrylate as the (co) polymer of principal component.
[23] a kind of resin-formed body, it includes (methyl) acrylic resin groups described in any one of [1]~[22] Close object.
[24] a kind of laminated resin body is that at least one surface of the resin-formed body described in [23] has solidification quilt The laminated resin body of the sheet of film (F),
Above-mentioned solidification envelope (F) is formed by the solidfied material of solidification compound (f), and the solidification compound (f) is contained Polyfunctional monomer (F1) with 3 or more (methyl) acryloyl groups and the polyfunctional monomer with 2 (methyl) acryloyl groups (F2)。
[25] laminated resin body according to [24], above-mentioned solidification compound (f) contain above-mentioned polyfunctional monomer (F1) 50 mass % or more, 80 mass % or less and above-mentioned polyfunctional monomer (F2) 20 mass % or more, 50 mass % or less.
[26] a kind of manufacturing method of (methyl) acrylic resin composition, is described in any one of [2]~[19] (methyl) acrylic resin composition manufacturing method, it includes following processes 1 and processes 2.
Process 1：In the mixture (X2) containing monomer composition (X1) and amphiphilic compound (E), the resistance of addition phosphorus system Come the process for obtaining polymerizable composition, polymerizable composition (X3), the monomer composition (X1) includes that side chain has aromatic hydrocarbyl for combustion agent (C) Or (methyl) acrylate (M) monomer of the alicyclic type hydrocarbon of carbon atom number 3~20.
Process 2：The process that above-mentioned polymerizable composition, polymerizable composition (X3) is polymerize.
[27] manufacturing method of (methyl) acrylic resin composition described in [20] is any in [20]~[22] The manufacturing method of (methyl) acrylic resin composition described in, in above-mentioned operation 1, said mixture (X2) contains two Parent's property compound (E) and impact resistance modifier (D), the impact resistance modifier (D) are selected from multiplet acrylic copolymer At least one of object particle (D1) or acrylic block copolymer (D2).
Multiplet acrylic acid series copolymer particle (D1)：With including the rubbery copolymer with cross-linked structure The multiplet acrylic acid series copolymer of the structure of hard resin layer (d1-2) is formed on the surface of elastomer particle (d1-1) Particle.
Acrylic block copolymer (D2)：With 10 mass % of methacrylate block (d2-1) or more, 60 matter Measure 90 mass % block copolymers below of % or less and acrylic ester polymerization block (d2-2) 40 mass % or more.
[28] manufacturing method of (methyl) acrylic resin composition according to [26] or [27], above-mentioned monomer group The gross mass of object (X1) relative to monomer composition (X1) is closed, includes 19.95 mass % of methyl methacrylate monomer or more 84.95 mass % or less and above-mentioned 3.6 mass % of (methyl) acrylate (M) or more, 80.0 mass % or less.
[29] manufacturing method of (methyl) acrylic resin composition according to [28], above-mentioned monomer composition (X1) there is the methacrylate (M1) and side chain of the alicyclic type hydrocarbon of aromatic hydrocarbyl or carbon atom number 3~20 comprising side chain The acrylate (M2) of alicyclic type hydrocarbon with aromatic hydrocarbyl or carbon atom number 3~20 is used as above-mentioned (methyl) acrylate (M), also,
Above-mentioned methacrylate (M1) be 10.0 mass % or more, 79.5 mass % hereinafter,
Above-mentioned acrylate (M2) is 0.50 mass % or more, 20.0 mass % or less.
[30] manufacturing method of (methyl) acrylic resin composition according to [28] or [29], above-mentioned monomer group Close object (X1) include molecule in 2 or more ethylenic unsaturated bonds 0.05 mass % of monomer (B) or more, 0.40 mass % with Under.
[31] manufacturing method of (methyl) acrylic resin composition according to any one of [26]~[30], on Monomer composition (X1) is stated in advance comprising the polymer containing the repetitive unit from above-mentioned (methyl) acrylate (M) (P1)。
[32] manufacturing method of (methyl) acrylic resin composition according to any one of [26]~[31], will Above-mentioned monomer composition (X1) is set as 100 mass parts, and above-mentioned polymerizable composition, polymerizable composition (X3) contains above-mentioned phosphorus flame retardant (C) 5.0 It is more than mass parts 35.0 below the mass with more than 0.01 mass parts of above-mentioned amphiphilic compound (E) 2.0 below the mass.
The effect of invention
By means of the invention it is possible to which steadily providing has good heat resistance, further with (methyl) of high flame retardant Acrylic resin composition, and the resin-formed body formed by above-mentioned (methyl) acrylic resin composition.
In addition, by means of the invention it is possible to steadily providing (methyl) acrylic acid with high flame retardant and high-impact Based resin composition, and the resin-formed body formed by above-mentioned (methyl) acrylic resin composition.
In addition, by means of the invention it is possible to steadily providing (methyl) acrylic acid with high flame retardant and high marresistance Based resin composition, and the resin-formed body formed by above-mentioned (methyl) acrylic resin composition.Such resin at Type body is suitable for the purposes that billboard etc. requires high flame retardant.
Detailed description of the invention
Fig. 1 is to change the spin lock time for locking cross polarization method by proton spin to detect13C core and31P core spectrum Pulse train.
Fig. 2 is the side cross-sectional view for indicating an example of laminated resin body of the invention.Indicate that solidification envelope is laminated in resin base The schematic diagram in the section of the laminated resin body on one surface of material.
Fig. 3 is the side cross-sectional view for indicating an example of laminated resin body of the invention.Indicate that solidification envelope is laminated in resin base The schematic diagram in the section of the laminated resin body on two surfaces of material.
Specific embodiment
Hereinafter, explaining the present invention in detail.In the present invention, " (methyl) acrylate " and " (methyl) acrylic acid " is respective It indicates selected from least one of " acrylate " and " methacrylate " and is selected from " acrylic acid " and " methacrylic acid " At least one of.
In addition, " monomer " indicates that unpolymerized compound, " repetitive unit " indicate the source formed by monomer polymerization In the unit of above-mentioned monomer.Repetitive unit can be the unit directly formed by polymerization reaction, be also possible to by that will gather Close that object is handled and a part of said units is changed into the units of other structures.
In addition, " quality % " indicates the content of scheduled ingredient included in 100 mass % of entire amount.
< (methyl) acrylic resin composition >
An example of embodiment as (methyl) acrylic resin composition of the invention is following (methyl) third Olefin(e) acid based resin composition, be containing aftermentioned (methyl) acrylic acid series polymeric compounds (P), aftermentioned phosphorus flame retardant (C) and (methyl) acrylic resin composition of aftermentioned amphiphilic compound (E), (methyl) acrylic resin composition are opposite In above-mentioned 100 mass parts of (methyl) acrylic acid series polymeric compounds (P), contain more than 5.0 mass parts of phosphorus flame retardant (C) 35.0 mass Part hereinafter, and more than 0.01 mass parts of aftermentioned amphiphilic compound (E) 2.0 below the mass, also, having in JIS K In the fire resistance test A method of 6911-1995 within 3 minutes self-extinguishment anti-flammability.
In addition, an example as other embodiments, is following (methyl) acrylic resin composition, be containing (methyl) propylene of (methyl) acrylic acid series polymeric compounds (P), aftermentioned phosphorus flame retardant (C) and aftermentioned amphipathic chemical combination (E) Sour based resin composition, above-mentioned (methyl) acrylic acid series polymeric compounds (P) are comprising from aftermentioned (methyl) acrylate (M) Repetitive unit polymer, the dispersion particle diameter of the phosphorus flame retardant (C) in (methyl) acrylic resin composition is 0.8 μm Hereinafter, also, have in the fire resistance test A method of JIS K 6911-1995 within 3 minutes self-extinguishment anti-flammability.
If (methyl) acrylic resin composition has the anti-flammability of the self-extinguishment within 3 minutes in above-mentioned test, Then due to when can prevent fire from occurring fire spreading, prolong burning, set out from a security point, be it is preferred, be suitble to It is used in identified ads board such as gasoline service station etc..
Above-mentioned (methyl) acrylic acid series polymeric compounds (P) can be set to comprising from aftermentioned (methyl) acrylate (M) Repetitive unit polymer.
< phosphorus flame retardant (C) >
In the present invention, in order to improve the anti-flammability of resin-formed body, (methyl) acrylic resin composition is preferably comprised Phosphorus flame retardant is as one of constituent.
The upper limit of the dispersion particle diameter of phosphorus flame retardant is not particularly limited, and becomes good from the anti-flammability of resin-formed body Viewpoint is set out, preferably 0.8 μm hereinafter, more preferably 0.1 μm hereinafter, further preferably 0.05 μm or less.Dispersion particle diameter Lower limit is not particularly limited, and dispersion particle diameter is smaller the more preferred.
The method of dispersion particle diameter as control phosphorus flame retardant (C), can enumerate for example, adjusting above-mentioned amphiphilic compound Type or content or above-mentioned (methyl) acrylate (M) type and aftermentioned (methyl) acrylic resin of addition The opportunity of the amphiphilic compound (E) and phosphorus flame retardant (C) recorded in the manufacturing method of composition.
In addition, above-mentioned dispersion particle diameter can be obtained by the measuring method of aftermentioned dispersion particle diameter.
In addition, in the present invention, so-called dispersion particle diameter is times for using optical microscopy to observe with 1000 times of multiplying power The dispersed particle of meaning or agglutination particle 20, measure the primary particle size of dispersed particle or the aggregate particle size of agglutination particle, and carry out Average value.In addition, so-called above-mentioned agglutination particle, refers to the offspring of dispersed particle (primary particle) contact and formation.
In such (methyl) acrylic resin composition, relative to above-mentioned (methyl) acrylic acid series polymeric compounds (P) 100 Mass parts, preferably can be containing more than above-mentioned phosphorus flame retardant (C) 5.0 mass parts 35.0 below the mass, more preferable 10.0 matter Measure part or more 30.0 below the mass, more than further preferred 15.0 mass parts 25.0 below the mass.
If the content of phosphorus flame retardant (C) is 5.0 relative to the lower limit of 100 mass parts of (methyl) acrylic acid series polymeric compounds More than mass parts, then the anti-flammability of resin-formed body becomes good.In addition, if the content of phosphorus flame retardant (C) is relative to (first Base) acrylic acid series polymeric compounds 100 the upper limits of mass parts be 35.0 below the mass that then the heat resistance of resin-formed body becomes good It is good.
As phosphorus flame retardant (C), phosphate based compound (hreinafter referred to as " phosphate " can be enumerated.), phosphonate ester system Compound (hreinafter referred to as " phosphonate ester ".).Specifically, may be exemplified compound below, but it is not limited to these chemical combination Object.These compounds can be used alone or use two or more together.
1) non-halogen phosphoric ester：
Monoethyl phosphate, phosphoric acid mono-n-butylester, acid phosphate methyl esters, acid phosphate ester, acid butyl phosphate, di(2-ethylhexyl)phosphate fourth Ester, trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), tricresyl phosphate The aromatic series such as (dimethylbenzene) ester (TXP), cresyl diphenyl phosphate (CDP), 2- ethylhexyl diphenyl phosphate (EHDP) Phosphate and their derivative compound, their condensation product.
The reaction product of phosphoryl chloride phosphorus oxychloride and binary phenol system compound and phenol (or alkyl phenol).Such as bis- (the hexichol of resorcinol Base phosphate), resorcinol bis- (two (xylyl) phosphates), the aromatic condensations phosphorus such as bisphenol-A bis- (diphenyl phosphoesters) Acid esters and their derivative compound, their condensation product.
2) phosphate containing halogen：Tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (chloropropyl) ester, tricresyl phosphate (two chloropropyls) ester, Tricresyl phosphate (dibromopropyl) ester, bis- (2,3- dibromopropyl) -2,3- dichloro propyl phosphates, bis- (chloropropyl) octyl phosphates Deng and their derivative compound, their condensation product.
3) phosphonate ester：Vinyl phosphonic dimethyl phthalate, vinyl phosphonic diethyl phthalate, vinyl phosphonic acid diphenyl, diphenyl Ethylene oxide phosphine etc. and their derivative compound, their condensation product.
As non-halogen phosphoric ester, can be used for example, north of the city chemistry (strain) system " JAMP-2 ", " JAMP-4 ", “JAMP-8”、“JAMP-12”、“JP-501”、“JP-502”、“JP-504”、“JP-504A”、“JP-506H”、“JP-508”、 "JP-512","JP-513","JP-518O","JP-524R","DBP","LB-58"；Big eight chemical industry (strain) system “TMP”、“TEP”、“TPP”、“TCP”、“TXP”、“CDP”、“PX-110”、“#41”、“CR-733S”、“CR-741”、“PX- 200 ", big eight chemical industry (strain) system can be used as phosphate containing halogen in " DAIGUARD-400/580/610 " The commercially available products such as " TMCPP ", " CRP ", " CR-900 ", " CR-504L ", " CR-570 ", " DAIGUARD-540 ".
As phosphonate ester, " V series " for example, piece mountain chemical industry (strain) system can be used, ball water chestnut oiling is industrial (strain) Commercially available products such as " Nonnen 73 " of system.
Even if passing through amphipathicization selected from least one of phosphate and phosphonate ester in above-mentioned phosphorus flame retardant (C) It closes object (E) and is easy to inhibit the formation of agglutination particle, as a result, the anti-flammability of resin-formed body becomes well, therefore preferred.Make For phosphate, specifically, phosphate containing halogen can be enumerated.
By the phosphorus flame retardant (C) with anti-flammability improvement effect, and from above-mentioned (methyl) acrylate (M) The synergy of repetitive unit and the structural unit from aftermentioned monomer (B), so as to improve the resistance of resin-formed body Combustion property.
< amphiphilic compound (E) >
(methyl) acrylic resin composition in the present invention include amphiphilic compound (E) as constituent it One.Anti-flammability can be obtained so that the agglutination particle of phosphorus flame retardant (C) is inhibited by the inclusion of amphiphilic compound (E) Excellent (methyl) acrylic resin composition.
Here, so-called amphiphilic compound, refer to 1 intramolecular have " hydrophilic group " and " hydrophobic group (lipophilic group) " this two The compound of person.Here, so-called " hydrophilic group " refers to compared with aftermentioned (methyl) acrylic acid series polymeric compounds (P), for phosphorus system Fire retardant (C) has the position of more high-affinity, so-called " hydrophobic group (lipophilic group) ", refers to compared with phosphorus flame retardant (C), right There is the position of more high-affinity in above-mentioned (methyl) acrylic acid series polymeric compounds (P).
By the inclusion of amphiphilic compound, it is still not clear so that the anti-flammability of resin-formed body becomes excellent reason, but Supposition is that the position of the hydrophilic group because of amphiphilic compound is easy to be coordinated with phosphorus flame retardant (C), hydrophobic group (lipophilic group) Position is easy to be coordinated with (methyl) acrylic acid series polymeric compounds (P), therefore phosphorus flame retardant (C) not formed agglutination particle, is easy to equal Even ground micro disperse is dissolved in resin combination.
The lower limit of the content of amphiphilic compound (E) is not particularly limited, from the not formed agglutination grain of phosphorus flame retardant (C) Son, from the perspective of the anti-flammability of resin-formed body becomes good, relative to above-mentioned (methyl) acrylic acid series polymeric compounds (P) 100 Mass parts, more than preferably 0.01 mass parts, more than more preferably 0.05 mass parts, more than further preferably 0.1 mass parts. The lower limit of the content of amphiphilic compound (E) is not particularly limited, from the anti-flammability that can be well maintained resin-formed body Viewpoint is set out, and preferably 2.0 below the mass, and more preferably 0.6 below the mass, and further preferably 0.3 below the mass.
In addition, in the present invention, as above-mentioned amphiphilic compound (E), by using anionic surfactant, from And the anti-flammability of resin-formed body can be made more excellent.Here, so-called anionic surfactant, referring to has yin in structure The compound of ionic hydrophilic group.The reason that the anti-flammability of resin-formed body becomes excellent is still not clear, but speculate be because The position of the hydrophilic group of the anionic property of anionic surfactant is easier to be coordinated with phosphorus flame retardant (C), therefore phosphorus system Fire retardant (C) not formed agglutination particle, is easy to more uniformly micro disperse or is dissolved in resin combination.
In addition, anionic surfactant is described in the explanation of above-mentioned amphiphilic compound (E), but Needless to say, naturally it is also possible to according to the structure of used phosphorus flame retardant (C), characteristic, use nonionic system surface-active Agent, anionic surfactant.
In addition, in the present invention, as above-mentioned anionic surfactant, carboxylate, sulfonate, sulfuric acid can be used Ester salt etc..Wherein, by using the alkali metal salt of alkyl sulfosuccinic, so as to keep the anti-flammability of resin-formed body more excellent It is different.
In addition, in the present invention, as the alkali metal salt of abovementioned alkyl sulfosuccinic acid, by using dioctyl sulfo group amber Meticortene Solu-Delta-cortef, so as to keep the anti-flammability of resin-formed body further excellent.
In addition, in the present invention, making by using selected from least one of phosphate containing halogen and phosphonate ester containing halogen For above-mentioned phosphorus flame retardant (C), also, use non-halogen phosphoric ester shown in following chemical formula (I) as above-mentioned amphipathicization It closes object (E), thus anti-flammability improvement effect excellent possessed by phosphate containing halogen or phosphonate ester containing halogen and amphipathicization The dispersed improvement effect for closing phosphorus flame retardant (C) possessed by object (E) complements each other, and can make the anti-flammability of resin-formed body It is further excellent.
(in formula (I), R indicates alkyl, naphthenic base, aryl, alkoxy, alkoxy carbonyl, alkyl carboxyl, alkylidene, sub- ring Alkyl, arlydene, aryl alkylene, polyoxyalkylenes, n are 1 or 2.)
Further, in the amphiphilic compound (E) shown in above-mentioned chemical formula (I), by keeping the R carbon in formula (I) former The aliphatic alkyl of subnumber 2~24, so that the dispersibility of phosphorus flame retardant (C) possessed by amphiphilic compound (E) improves effect Fruit becomes better, therefore the anti-flammability of resin-formed body can be made more excellent.
< (methyl) acrylic acid series polymeric compounds (P) >
(methyl) acrylic resin composition in the present invention includes following (methyl) acrylic acid series polymeric compounds (P) conducts One of constituent.By the inclusion of above-mentioned (methyl) acrylic acid series polymeric compounds (P) one of as constituent, thus by with it is rear The synergy for other constituents stated can obtain (methyl) the acrylic resin molding of heat resistance and excellent in flame retardance Body.
(methyl) acrylic acid series polymeric compounds (P) can be used comprising having aromatic hydrocarbyl or carbon atom number from side chain The polymer of the repetitive unit of (methyl) acrylate (M) of 3~20 alicyclic type hydrocarbon.
(methyl) acrylic acid series polymeric compounds (P) by the inclusion of derive from (methyl) acrylate (M) repetitive unit, thus The anti-flammability of resin-formed body improves, and by the effect of above-mentioned amphiphilic species (E), is able to suppress phosphorus flame retardant (C) Form agglutination particle.
Further in above-mentioned (methyl) acrylic acid series polymeric compounds (P), it may include from methyl methacrylate Repetitive unit, the repetitive unit from above-mentioned (methyl) acrylate (M) and aftermentioned derive from have 2 in molecule The structural unit of the monomer (B) of the above ethylenic unsaturated bond.
(methyl) acrylic acid series polymeric compounds (P) by the inclusion of derive from methyl methacrylate repetitive unit, so as to Enough make heat resistance and the weatherability of resin-formed body excellent, and mechanical strength, thermal property, molding processibility are more excellent.
(methyl) acrylic acid series polymeric compounds (P) are by the inclusion of the structural unit for deriving from monomer (B), so as to make resin Anti-flammability, heat resistance, the mechanical property of formed body are more excellent.
Lower limit from the content of the repetitive unit of methyl methacrylate is not particularly limited, from resin-formed body Impact resistance, mechanical strength become well to set out, preferably 19.95 mass % or more, more preferably 40.0 mass % or more, into One step is preferably 50.0 mass % or more.In addition, the upper limit of content is not particularly limited, become from the anti-flammability of resin-formed body From the perspective of good, preferably 84.95 mass % are hereinafter, more preferably 82.0 mass % are hereinafter, further preferably 79.1 Quality % or less.Above-mentioned upper limit value and lower limit value can be in 100 matter of gross mass for being no more than (methyl) acrylic acid series polymeric compounds (P) In the range of measuring %, arbitrarily combine.
< (methyl) acrylate (M) >
In the present invention, so-called (methyl) acrylate (M) has aromatic hydrocarbyl or carbon atom number 3~20 for side chain Alicyclic type hydrocarbon simple function (methyl) acrylate.By containing (methyl) acrylate (M), thus resin-formed body Anti-flammability become good.
As concrete example, (methyl) cyclohexyl acrylate, (methyl) acrylic acid borneol base ester, (methyl) acrylic acid can be enumerated Norbornane base ester, (methyl) isobornyl acrylate, (methyl) adamantyl acrylate, (methyl) acrylic acid dimethyl The own ester of adamantane esters, trimethyl cyclohexyl methacrylate, (methyl) acrylic acid norborneol alkyl methacrylate ester, (methyl) acrylic acid peppermint Base ester, (methyl) acrylic acid fenchyl ester, (methyl) dicyclopentanyl acrylate, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) Acrylic acid dicyclopentenyl oxygroup ethyl ester, (methyl) acrylic acid cyclodecyl ester, (methyl) acrylic acid 4- t-butylcyclohexyl base ester, (the first such as (methyl) trimethylcyclohexylacrylate, (methyl) benzyl acrylate, (methyl) phenoxy ethyl acrylate Base) acrylate and their derivative.They can be used alone or use two or more together.
If applying heat, side chain is detached from above-mentioned (methyl) acrylate (M), is converted to methacrylic acid structural unit. The methacrylic acid structural unit, phosphorus flame retardant (C) work, by its synergy, thus the generation of carbide (charcoal) Amount increases.In addition, by plus the monomer (B) with 2 or more vinyl, to further promote the generation of charcoal.Carbide The anti-flammability of (charcoal) raising resin combination.
Further, there is bulky side chain from the repetitive unit of above-mentioned (methyl) acrylate (M), the volume is big Side chain by decompose be detached from, generate volatile ingredient, thus make burn place oxygen concentration reduce, resin combination it is fire-retardant Property becomes excellent.The decomposition of the bulky side chain, which can use, for example to be promoted by the thermal energy of burning generation.Further, if Above-mentioned phosphorus flame retardant (C) is added to resin combination in advance, then the decomposition product of phosphorus flame retardant (C) promotes above-mentioned volume big Side chain decomposition, the anti-flammability of resin combination can be made to become excellent.
In (methyl) acrylic resin composition of the invention, make it is using the measurement of following measuring methods 1, from upper State the half width (hreinafter referred to as " peak of decomposition product at the peak of the decomposition product of the repetitive unit of (methyl) acrylate (M) Half width ".) the upper limit be 26 DEG C hereinafter, so as to make (methyl) acrylic resin composition and by above-mentioned (methyl) The anti-flammability of the resin-formed body of acrylic resin composition manufacture becomes excellent.The half width at the peak of decomposition product is more preferable 21 DEG C are set as hereinafter, being further preferably set as 19 DEG C or less.The lower limit of the half width at the peak of decomposition product is not particularly limited, excellent It is selected as 5 DEG C or more, more preferably 10 DEG C or more.
1 > of < measuring method
Using gas analysis measurement device (EGA-MS) occurs, by (methyl) acrylic resin composition 2mg in helium Under atmosphere (flow velocity 20ml/ minutes), with 10 DEG C/min of heating rate, the mass spectral analysis of the generation gas of decomposition product is carried out, is asked The half width at the peak of the decomposition product in temperature-chromatographic curve obtained out.
The half width at the peak of decomposition product can be by adjusting the monomeric unit of composition (methyl) acrylic acid series polymeric compounds (P) Type, the content of above-mentioned monomeric unit, type, the content of phosphorus flame retardant (C) etc. controlled.
Further, in (methyl) acrylic resin composition of the invention, by it is being obtained according to following measuring methods 2, The decomposition product of the repetitive unit from (methyl) acrylate (M) in above-mentioned (methyl) acrylic acid series polymeric compounds (P) Generate temperature Tc (unit：DEG C) and above-mentioned phosphorus flame retardant (C) decomposition product generation temperature Tm (unit：DEG C) calculate | Tm-Tc | value be to indicate the index of the easiness of the generation of decomposition (disengaging) gas of (methyl) acrylic resin composition, The value is smaller, then the anti-flammability of (methyl) acrylic resin composition becomes the better.| Tm-Tc | value can pass through selection The type of (methyl) acrylate (M) and phosphorus flame retardant (C) is controlled.
In resin-formed body of the invention, pass through the decomposition of the repetitive unit from above-mentioned (methyl) acrylate (M) The generation temperature of the decomposition product of product and above-mentioned phosphorus flame retardant (C) meets following formula (1), so as to make resin-formed body Anti-flammability and heat resistance become better.
If | Tm-Tc | the upper limit be 40 hereinafter, if the anti-flammability of resin-formed body become well, therefore it is preferred, it is more excellent 20 are selected as hereinafter, further preferably 10 or less.| Tm-Tc | lower limit be not particularly limited, as long as more than 0.
|Tm-Tc|≤40 ···(1)
Tc：Generation temperature (the unit of phosphorus flame retardant (C) decomposition product：℃)
Tm：From the generation temperature (unit of the decomposition product of the repetitive unit of (methyl) acrylate (M)：℃)
2 > of < measuring method
Using gas analysis measurement device (EGA-MS) occurs, by (methyl) acrylic resin composition 2mg in helium Under atmosphere (flow velocity 20ml/ minutes), with 10 DEG C/min of heating rate, the mass spectral analysis of the generation gas of decomposition product is carried out, is found out The generation temperature of decomposition product in temperature-chromatographic curve of acquisition.
Further, in (methyl) acrylic resin composition of the invention, by it is being obtained by said determination method 2, on State the generation temperature of the decomposition product of the repetitive unit from methyl methacrylate in (methyl) acrylic acid series polymeric compounds (P) Degree is set as Ta (unit：DEG C) when, " Ta-Tm " (unit：DEG C) value indicate as (methyl) acrylic resin composition The temperature and origin that main decomposition products, repetitive unit from above-mentioned methyl methacrylate decomposition product generates Side chain in the repetitive unit of above-mentioned (methyl) acrylate (M) and the temperature difference for the temperature that the decomposition product come generates Index.
The value of " Ta-Tm " is bigger, then the main decomposition products as above-mentioned (methyl) acrylic resin composition, Before generating from the decomposition product of the repetitive unit of above-mentioned methyl methacrylate, origin is derived from above-mentioned (methyl) acrylic acid Side chain in the repetitive unit of ester (M) and the decomposition product come generates, therefore the anti-flammability of resin-formed body becomes the better.
The value of " Ta-Tm " can suitably select the copolymerization of above-mentioned (methyl) acrylic acid series polymeric compounds (P) to form, above-mentioned (first Base) type of the additives such as type, molecular weight, crosslinking agent of acrylate (M) controlled.
Here, so-called " the main decomposition object of (methyl) acrylic resin composition " refers in addition to origin is derived from above-mentioned Side chain in the repetitive unit of (methyl) acrylate (M) and other than the decomposition product that comes, the combination of (methyl) acrylic resin The decomposition product of object.
In resin-formed body of the invention, from the decomposition product of the repetitive unit of above-mentioned (methyl) acrylate (M) Meet following formula (2) with the generation temperature of the decomposition product of the repetitive unit from above-mentioned methyl methacrylate.
The lower limit of " Ta-Tm " is not particularly limited, and if it is 100 or more, the anti-flammability of resin-formed body becomes well, Therefore preferably, more preferably 110 or more, further preferably 115 or more.The upper limit of " Ta-Tm " is not particularly limited, from preventing From (methyl) acrylate (M) repetitive unit side chain decompose, be detached from temperature low temperature and anti-flammability becomes not fill From the perspective of point, preferably 200 or less.
100≤Ta-Tm ···(2)
Ta：From the generation temperature (unit of the decomposition product of the repetitive unit of methyl methacrylate：℃)
Lower limit from the content of the repetitive unit of (methyl) acrylate (M) is not particularly limited, from resin forming From the perspective of the anti-flammability of body becomes good, preferably 3.6 mass % or more, more preferably 15.0 mass % or more, into one Step is preferably 20.5 mass % or more.The upper limit of content is not particularly limited, impact resistance, mechanical strength from resin-formed body From the perspective of becoming good, preferably 80.0 mass % hereinafter, more preferably 60.0 mass % hereinafter, further preferably 40.0 mass % or less.Above-mentioned upper limit value and lower limit value can be in the gross masses for being no more than (methyl) acrylic acid series polymeric compounds (P) In the range of 100 mass %, arbitrarily combine.
As (methyl) acrylic acid series polymeric compounds (P) for containing above-mentioned (methyl) acrylate (M), can be used comprising coming There is the repetitive unit of the methacrylate (M1) of the ester ring type hydrocarbon of aromatic hydrocarbon or carbon atom number 3~20 derived from side chain, and There is the repetitive unit of the acrylate (M2) of the alicyclic type hydrocarbon of aromatic hydrocarbyl or carbon atom number 3~20 from side chain (methyl) acrylic acid series polymeric compounds (P).
In addition, methacrylate (M1) and acrylate (M2) and phosphorus flame retardant (C) interact, have synergistically The effect of anti-flammability improvement effect possessed by phosphorus flame retardant (C) is improved, therefore can be improved the anti-flammability of resin-formed body.
In addition, by the inclusion of acrylate (M2), thus in (methyl) acrylic resin composition after polymerization not Reaction monomers are reduced, therefore the weatherability of the resin-formed body obtained becomes good.
As (methyl) acrylic acid series polymeric compounds (P) for containing above-mentioned (methyl) acrylate (M), can be used comprising coming 10.0 mass % of repetitive unit or more, 79.5 mass % derived from above-mentioned methacrylate (M1) is hereinafter, and from above-mentioned third 0.50 mass % of repetitive unit or more, the 20.0 mass % of olefin(e) acid ester (M2) is hereinafter, and include from above-mentioned methacrylic acid The repetitive unit of ester (M1) and 15.0 mass % or more 80.0 are added up to from the repetitive unit of above-mentioned acrylate (M2) Quality % (methyl) acrylic acid series polymeric compounds (P) below.
Lower limit from the content of the repetitive unit of methacrylate (M1) is not particularly limited, from resin-formed body Anti-flammability and from the perspective of heat resistance becomes good, preferably 10.0 mass % or more, more preferably 20.0 mass % with On.In addition, the upper limit about content, is not particularly limited, it is excellent from the viewpoint of the weatherability of resin-formed body becomes good 79.5 mass % are selected as hereinafter, more preferably 70.0 mass % or less.Above-mentioned upper limit value and lower limit value can be combined arbitrarily.
Lower limit from the content of the repetitive unit of acrylate (M2) is not particularly limited, from the resistance of resin-formed body From the perspective of combustion property and weatherability become good, preferably 0.50 mass % or more, more preferably 1.0 mass % or more.Contain The upper limit of amount is not particularly limited, from the viewpoint of the heat resistance of resin-formed body becomes good, preferably 20 mass % with Under, more preferably 6.0 mass % or less.Above-mentioned upper limit value and lower limit value can be combined arbitrarily.
The content of repetitive unit from methacrylate (M1) and the repetitive unit from acrylate (M2) Total lower limit be not particularly limited, from the viewpoint of the anti-flammability of resin-formed body becomes good, preferably 15.0 matter Measure % or more, more preferably 20.5 mass % or more.The upper limit of content is not particularly limited, from the heat resistance of resin-formed body and From the perspective of weatherability becomes good, preferably 80.0 mass % are hereinafter, more preferably 40.0 mass % or less.The above-mentioned upper limit Value and lower limit value can be combined arbitrarily.
In (methyl) acrylic resin composition of the invention, the sight excellent from the improvement effect of anti-flammability and heat resistance Point sets out, and above-mentioned methacrylate (M1) can be used selected from cyclohexyl methacrylate and isobornyl methacrylate At least one of.
In (methyl) acrylic resin composition of the invention, the sight excellent from the improvement effect of anti-flammability and weatherability Point sets out, and above-mentioned acrylate (M2) can be used selected from least one of cyclohexyl acrylate and isobornyl acrylate (hereinafter, " monomer (m2) ").
By the inclusion of monomer (m2), so as to be further reduced in (methyl) acrylic resin composition after polymerization Unreacted monomer, the weatherability of resin forming becomes better.Further, monomer (m2) and phosphorus flame retardant (C) phase interaction With, have the effect of synergistically improve phosphorus flame retardant (C) possessed by anti-flammability improvement effect, therefore can be improved resin at The anti-flammability of type body.
The lower limit of the content of monomer (m2) is not particularly limited, by relative to above-mentioned (methyl) acrylic acid series polymeric compounds (P) 100 mass parts are set as 1.0 mass % or more, so as to make anti-flammability and the weatherability of resin-formed body become better, Therefore preferably, more preferably 2.0 mass % or more.On the other hand, the upper limit of content is not particularly limited, if content is 4.99 Quality % is hereinafter, can then further increase the heat resistance of resin-formed body, therefore preferably, more preferably 4.0 mass % or less. Above-mentioned upper limit value and lower limit value can be combined arbitrarily.
< monomer (B) >
Monomer (B) is the monomer with 2 or more vinyl, is (methyl) acrylic resin composition of the invention One of constituent.By making (methyl) acrylic resin composition contain monomer (B), so as to further increase resin The anti-flammability of formed body.
By the structural unit that (methyl) acrylic acid series polymeric compounds (P) include from monomer (B), so as to make resin Anti-flammability, heat resistance, the mechanical property of formed body are more excellent.
Lower limit from the content of the structural unit of above-mentioned monomer (B) is not particularly limited, from the resistance of resin-formed body From the perspective of combustion property becomes good, more than preferably 0.05 mass parts, more than more preferably 0.12 mass parts.In addition, content The upper limit be not particularly limited, from the viewpoint of the impact resistance of resin-formed body, mechanical strength become good, preferably 0.40 below the mass, and more preferably 0.36 below the mass.Above-mentioned upper limit value and lower limit value can be no more than (methyl) third In the range of the 100 mass % of gross mass of olefin(e) acid based polymer (P), arbitrarily combine.
As monomer (B), preferably two functions (methyl) acrylate.Such as ethylene glycol two (methyl) acrylic acid can be enumerated Ester, 1,2- propylene glycol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, 1,6-HD two (methyl) third Two (the first of alkane glycol such as olefin(e) acid ester, neopentyl glycol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate Base) acrylate.They can be used alone or use two or more together.
In above-mentioned monomer (B), the monomer of carbon atom number 10~14 can be improved since the operability of raw material is good Manufacture operability when (methyl) acrylic resin composition.
Further, if it is in ethylene glycol two (methyl) acrylate and neopentyl glycol two (methyl) acrylate At least one monomer, then the operability of raw material is excellent, in addition to this, the anti-flammability of resin-formed body can be made more excellent, therefore It is preferred that.
The monomer > that < can be copolymerized
In the present invention, can according to need makes acrylic acid series polymeric compounds (P) relative to (methyl) acrylic polymeric 100 mass % of object (P) is 0 mass % or more, 12 mass % hereinafter, preferably 0.8 mass % or more, 9.0 mass % model below It encloses containing the monomer that can be copolymerized with methyl methacrylate and (methyl) acrylate (M).
As the monomer that can be copolymerized with methyl methacrylate and (methyl) acrylate (M), (methyl) third can be enumerated Olefin(e) acid ethyl ester, (methyl) isopropyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) propylene The acid anhydrides, N- benzene such as unsaturated carboxylic acids, maleic anhydride, the itaconic anhydrides such as sour N-butyl, (methyl) acrylic acid, maleic acid, itaconic acid The second such as maleimide derivatives, vinyl acetate, the vinyl benzoates such as base maleimide, N- N-cyclohexylmaleimide The nitrogen containing monomers, (methyl) third such as alkenyl esters, vinyl chloride, vinylidene chloride and their derivative, Methacrylamide, acrylonitrile The aromatic ethenyls such as the monomer containing epoxy group such as olefin(e) acid glycidyl acrylate and styrene, α-methylstyrene Compound.
< (methyl) acrylic resin composition >
For the value D being calculated by following formula (a) of (methyl) acrylic resin composition of the invention1(%), It can be when making spin lock time τ=30msec, by value D1(%) is set as 6% or less.In following formula (a), MC (τ) and MP (τ) is the intensity for the relaxation spectrum observed using solid NMR measurement device using spin lock cross polarization method, can be by rear Method is stated to measure.
D1(%)=| MC (τ)-MP (τ) |/MC (τ) (a)
MC(τ)：The average value of the value of following (A) and (B)
When (A) by spin lock time τ sec13The carbon with carbonyl that 160ppm~180ppm of C nuclear ralaxation spectrum is observed When the area of corresponding spectrum is divided by 10 μ sec of spin lock time13160ppm~180ppm of C nuclear ralaxation spectrum is observed The carbon with carbonyl corresponding to spectrum the obtained value of area.
When (B) by spin lock time τ sec13The carbon with methylene that 30ppm~65ppm of C nuclear ralaxation spectrum is observed When the area of corresponding spectrum is divided by 10 μ sec of spin lock time13What 30ppm~65ppm of C nuclear ralaxation spectrum was observed The value that the area of spectrum corresponding to carbon with methylene obtains.
MP(τ)：When by spin lock time τ sec31- 40~40ppm of P nuclear ralaxation spectrum is observed and phosphorous flame-retardant When the area of spectrum corresponding to the phosphorus atoms of agent (C) is divided by 10 μ sec of spin lock time31- 40~40ppm institute of P core spectrum The value that the area of spectrum corresponding to the phosphorus atoms with phosphorus flame retardant (C) observed obtains.
Further, for the value being calculated by above-mentioned formula (a) of (methyl) acrylic resin composition of the invention D1(%), each value D when spin lock time τ=16msec, 20msec, 25msec, 30msec1The average value D of (%)2(%) It can be set to 7% or less.
Here, the carbon of the carbonyl of so-called (methyl) acrylic resin composition is poly- with above-mentioned (methyl) acrylic acid series Close the carbon of the carbonyl in the ester side chain of the α carbon phase neighbour in object (P).It says in further detail, is and above-mentioned (methyl) acrylic acid series The repetitive unit from methyl methacrylate in polymer (P), the repetition from above-mentioned methacrylate (M1) The ester ring type of the carbon atom number 3~20 of unit or the α carbon phase neighbour in the repetitive unit of above-mentioned methacrylate (M2) Alkyl, aromatic hydrocarbyl side chain in carbonyl carbon.
It is the phosphorus of phosphate when phosphorus flame retardant (C) is phosphate in addition, the phosphorus atoms of so-called phosphorus flame retardant (C) Atom is the phosphorus atoms of phosphonic acid base when for phosphonate ester.
From phosphorus flame retardant (C) not being locally present in (methyl) acrylic resin composition, but it is equably molten From the perspective of solution or micro disperse, the weight average molecular weight of above-mentioned phosphate and phosphonate ester is preferably 200 or more 500 or less.
Peak corresponding to the carbon with carbonyl of (methyl) acrylic resin composition is according to (methyl) acrylic resin The difference of the composition of composition and it is different, for example, use comprising from side chain have aromatic hydrocarbyl or carbon atom number 3~ The polymer of the repetitive unit of (methyl) acrylate (M) of 20 alicyclic type hydrocarbon is as above-mentioned (methyl) acrylic polymeric In the case where object (P),13- 180ppm~-160ppm of C nuclear ralaxation spectrum is nearby observed.
It is different according to the difference of the type of phosphorus flame retardant (C) from peak corresponding to the phosphorus atoms of phosphorus flame retardant (C), For example, in phosphate or phosphonate ester,31- 10~10ppm of P nuclear ralaxation spectrum is nearby observed.
MC (τ) is the numerical value of the motility for the molecule that reflection constitutes (methyl) acrylic acid series polymeric compounds (P), and MP (τ) is anti- Reflect the numerical value for constituting the motility of molecule of phosphorus flame retardant (C).If phosphorus flame retardant (C) is dissolved with 5nm range below Or micro disperse in (methyl) acrylic acid series polymeric compounds (P), then the value of MC (τ) and MP (τ) is almost consistent.If phosphorus flame retardant (C) dispersed with the range of the size of 5nm or more, then the difference of the value of MC (τ) and MP (τ) increases.The value of MC (τ) and the value of MP (τ) Difference it is smaller, then phosphorus flame retardant (C) more not being locally present in (methyl) acrylic resin composition, but equably Dissolution or micro disperse, therefore keep the fire-retardant improvement effect of phosphorus flame retardant (C) more excellent.
The inventors of the present invention have found, as the phosphorus flame retardant (C) in regulation (methyl) acrylic resin composition The index of dissolved state or micro disperse state, D shown in above-mentioned formula (a)1When (%) is 6% or less, phosphorus flame retardant (C) will not Being locally present and equably dissolve or micro disperse, significantly show the anti-flammability improvement effect of phosphorus flame retardant (C), therefore show The anti-flammability of (methyl) acrylic resin composition significantly excellent such effect out.For being calculated by above-mentioned formula (a) The value D arrived1(%), the average value D of each value D when spin lock time τ=16msec, 20msec, 25msec, 30msec2(%) When being 7% or less, which becomes more excellent.
, it can be said that above-mentioned (methyl) acrylic resin composition, by using aftermentioned (methyl) acrylic resin The manufacturing method of composition, thus with only will simply be kneaded as the phosphorus flame retardant of fire retardant (C) to (methyl) acrylic acid Previous resin combination obtained by based polymer is compared, phosphorus flame retardant (C) will not being locally present and equably dissolve or Micro disperse, thus burning when, fire retardant equally works, thus there is a phenomenon where anti-flammability significantly increase it is such.
< impact resistance modifier (D) >
It, can be in (methyl) acrylic resin composition in order to improve the impact resistance of resin-formed body in the present invention In comprising as impact resistance modifier (D) selected from aftermentioned multiplet acrylic acid series copolymer particle (D1) or aftermentioned third At least one of olefin(e) acid based block copolymer (D2) compound is as one of constituent.
In (methyl) acrylic resin composition of the invention, relative to above-mentioned (methyl) acrylic acid series polymeric compounds (P) 100 mass parts may include above-mentioned 2.0 mass parts of impact resistance modifier (D) or more 50.0 below the mass.If impact resistance changes Content into agent (D) relative to the lower limit of 100 mass parts of (methyl) acrylic acid series polymeric compounds is 2.0 mass parts or more, then resin The impact resistance of formed body becomes well, therefore preferably, more than more preferably 5.0 mass parts.In addition, if impact resistance modifier (D) content is 50.0 below the mass then resin forming relative to the upper limit of 100 mass parts of (methyl) acrylic acid series polymeric compounds The anti-flammability and weatherability of body become well, therefore preferably, more preferably 30.0 below the mass, further preferably 20.0 matter Measure part or less.
< multiplet acrylic acid series copolymer particle (D1) >
At least one layer of above-mentioned multiplet acrylic acid series copolymer particle (D1) used in the present invention includes elastomer Particle (d1-1), the elastomer particle (d1-1) contain the rubbery copolymer layer with cross-linked structure.As long as having The copolymer particle of the rubbery copolymer layer of crosslinking structure, then each layer of multiplet acrylic acid series copolymer particle (D1) Composition, partial size is not limited.
For example, following multiplet acrylic acid series copolymer particle (D1-1) can be enumerated, have in above-mentioned elastomer grain The structure of hard resin layer (d1-2) is formed on the outside of sub (d1-1).
Further, it can enumerate and be formed with the hard resin with cross-linked structure on the inside of above-mentioned elastomer particle (d1-1) The multiplet acrylic acid series copolymer particle (D1-2) of layer (d1-3).
In addition, can enumerate in the inside of above-mentioned hard resin layer (d1-2), and the outside of above-mentioned hard resin layer (d1-2), It is formed further with the multiplet acrylic acid series copolymer particle (D1-3) of hard resin layer (d1-4).
< multiplet acrylic acid series copolymer particle (D1-1) >
As above-mentioned multiplet acrylic acid series copolymer particle (D1-1), can be used comprising with cross-linked structure On the surface of the elastomer particle (d1-1) of rubbery copolymer, graft polymerization hard resin ingredient and form hard resin layer (d1-2) multiplet acrylic acid series copolymer particle (D1-1).
(elastomer particle：d1-1)
As the rubbery copolymer for constituting above-mentioned elastomer particle (d1-1), can enumerate will be from alkyl acrylate (co) polymer of the repetitive unit as principal component.
Specifically, the repetitive unit 70~90 for the alkyl acrylate for being 1~8 comprising the carbon atom number from alkyl Quality %, from aromatic vinyl monomer repetitive unit 10~30 mass % and the list that can be copolymerized from other The (co) polymer of 0~20 mass % of repetitive unit of body.
The alkyl acrylate that carbon atom number as abovementioned alkyl is 1~8, can enumerate methyl acrylate, acrylic acid second Ester, isopropyl acrylate, n-butyl acrylate, 2-EHA etc..These monomers can be used alone or using 2 kinds with On use.
As above-mentioned aromatic vinyl monomer, styrene, α-methylstyrene, vinyltoluene etc. can be enumerated.These Monomer can be used alone or using two or more come using.
As the above-mentioned monomer that other can be copolymerized, methyl methacrylate, ethyl methacrylate, methyl-prop can be enumerated The vinyl cyanides such as the methacrylates such as olefin(e) acid phenyl ester, cyclohexyl methacrylate, benzyl methacrylate, (methyl) acrylonitrile Based compound etc..Further, it is also possible to include following polyfunctional monomers.
As above-mentioned polyfunctional monomer, ethylene glycol two (methyl) acrylate, 1,3- butylene two (methyl) propylene can be enumerated Acid esters, triethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, (methyl) allyl acrylate, two The crosslinking agents such as vinyl benzene, trimethylolpropane trimethacrylate, Triallyl isocyanurate, pentaerythritol tetraacrylate Equal crosslinking agents.These monomers can be used alone or using two or more come using.
The mass median diameter of above-mentioned elastomer particle (d1-1) is not particularly limited, it is however generally that, it is 100~300nm.
(hard resin layer：d1-2)
The hard resin ingredient for forming above-mentioned hard resin layer (d1-2), which may include, will derive from methacrylate (co) polymer of the repetitive unit as principal component.
Specifically, for the repetitive unit for the alkyl methacrylate for being 1~4 comprising the carbon atom number from alkyl 50 mass % or more, 100 mass % or less, from alkyl carbon atom number be 1~8 alkyl acrylate repetitive unit 0 Quality % or more 50 mass % or less and 0 mass % of repetitive unit or more, 20 matter from other monomers that can be copolymerized Measure % (co) polymer below.
The alkyl methacrylate that carbon atom number as abovementioned alkyl is 1~4, can enumerate for example, methacrylic acid The methyl acrylic esters such as methyl esters, ethyl methacrylate, propyl methacrylate, n-BMA；Acrylic acid first Esters of acrylic acid such as ester, ethyl acrylate etc..These monomers can be used alone or using two or more come using.
0~50 matter of repetitive unit as the alkyl acrylate that the carbon atom number from abovementioned alkyl is 1~8 % is measured, can be used is made with the elastomer particle (d1-1) comprising the rubbery copolymer with cross-linked structure previously enumerated The same substance of example.
As the monomer that other can be copolymerized, the aromatic series second such as styrene, α-methylstyrene, vinyltoluene can be enumerated Alkenyl monomer；The non-Arrcostab of the methacrylic acids such as phenyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, And non-Arrcostab of acrylic acid corresponding with them etc..Further, it is also possible to include above-mentioned polyfunctional monomer.
< multiplet acrylic acid series copolymer particle (D1-2) >
Above-mentioned multiplet acrylic acid series copolymer particle (D1) used in the present invention can be used in above-mentioned elastomer The multiplet acrylic acid series copolymer of the hard resin layer (d1-3) with cross-linked structure is formed on the inside of particle (d1-1) Particle (D1-2).
(the hard resin layer with cross-linked structure：d1-3)
As the hard resin ingredient for forming above-mentioned hard resin layer (d1-3), can enumerate will derive from the carbon atom of alkyl (co) polymer of the repetitive unit for the alkyl methacrylate that number is 1~4 as principal component.
As the hard resin ingredient for forming hard resin layer (d1-3), can be and above-mentioned hard resin layer (d1-2) phase Same resin component is also possible to different resin components.
Specifically, the repetition for the alkyl methacrylate for being 1~4 comprising the carbon atom number from alkyl can be enumerated 40 mass % of unit or more, 100 mass % or less, from alkyl carbon atom number be 1~8 alkyl acrylate repetition 0 mass % of unit or more, 60 mass % or less and 0 mass % of repetitive unit or more 20 from other monomers that can be copolymerized Quality % or less and 0.1 mass % of repetitive unit or more, 10 mass % (co) polymer below from polyfunctional monomer. By making composition in above-mentioned each range, so that it is whitening resistance to can get excellent falling sphere/hammer falling impact strength, impact resistance.
Used in the hard resin layer (d1-3) with cross-linked structure, the methyl-prop that the carbon atom number of alkyl is 1~4 Olefin(e) acid Arrcostab, alkyl carbon atom number be 1~8 alkyl acrylate, other monomers and polyfunctional monomer that can be copolymerized The same substance of hard resin layer (d1-2) that can be used and previously enumerate.
Above-mentioned hard resin layer (d1-3) when above-mentioned elastomer particle (d1-1) is set as 100 mass parts is not limited especially System, it is however generally that below the mass for more than 30 mass parts 100.
< multiplet acrylic acid series copolymer particle (D1-3) >
Above-mentioned multiplet acrylic acid series copolymer particle (D1) used in the present invention can be used in above-mentioned multiple knot Hard tree is formed further on the outside of the hard resin layer (d1-2) of structure acrylic acid series copolymer particle (D1-1) or (D1-2) The multiplet acrylic acid series copolymer particle (D1-3) of rouge layer (d1-4).
(hard resin layer：d1-4)
As the hard resin ingredient for forming above-mentioned hard resin layer (d1-4), can enumerate will be from methyl methacrylate (co) polymer of the repetitive unit of ester as principal component.
It is the methyl for being 1~4 comprising the carbon atom number from alkyl specifically, being following (co) polymer 50~100 mass % of repetitive unit of alkyl acrylate, from alkyl carbon atom number be 1~8 alkyl acrylate 0~50 mass % of repetitive unit and from aromatic vinyl monomer 0~20 mass % of repetitive unit it is (total) poly- Close object, and the glass transition temperature (hereinafter referred to as " Tg " of hard resin layer (d1-4).) it is 20~80 DEG C, it is harder than above-mentioned The Tg of matter resin layer (d1-2) is low.
As multiplet acrylic acid series copolymer particle (D1) other than the above, can obtain for example, the beautiful sun of Mitsubishi The W-341 of (strain) system, the commercially available products such as M-210 of (strain) Kaneka.
In addition, above-mentioned multiplet acrylic acid series copolymer particle (D1) can be manufactured by well known method.
From the viewpoint of the raising of the impact resistance of resin-formed body, in above-mentioned (methyl) acrylic resin composition The lower limit of the content of multiplet acrylic acid series copolymer particle (D1), relative to above-mentioned (methyl) acrylic acid series polymeric compounds (P) 100 mass parts are preferably 2.0 mass parts or more, more than more preferably 5.0 mass parts.From the resistance for being well maintained resin-formed body From the perspective of combustion property and weatherability, the upper limit of the content of multiplet acrylic acid series copolymer particle (D1) is preferably 20 mass Part hereinafter, more preferably 15 below the mass.
< acrylic block copolymer (D2) >
Above-mentioned acrylic block copolymer (D2) used in the present invention includes to have methacrylate block (d2-1) and the acrylic block copolymer of acrylic ester polymerization block (d2-2).Specifically, can enumerate with methyl-prop 10 mass % of olefine acid ester polymer block (d2-1) or more, 60 mass % or less and acrylate polymer block (d2-1) 40 matter Measure 90 mass % of % or more acrylic block copolymer below.
It further, include alkyl acrylate and (methyl) acrylic acid virtue in above-mentioned acrylate polymer block (d2-2) In the case where fragrant race's ester, above-mentioned acrylate polymer block (d2-2) preferably comprises the structure list from alkyl acrylate 50~90 mass % of member and 50~10 mass % of structural unit for deriving from (methyl) acrylic acid aromatic ester.
As acrylic block copolymer (D2) other than the above, can obtain for example, what Kuraray (strain) made Commercially available products such as " KURARITY ".
Under content about the acrylic block copolymer (D2) in above-mentioned (methyl) acrylic resin composition Limit, from the viewpoint of the raising of the impact resistance of resin-formed body, relative to above-mentioned (methyl) acrylic acid series polymeric compounds (P) 100 Mass parts, more than preferably 2.0 mass parts, more than more preferably 5.0 mass parts.About acrylic block copolymer (D2) The upper limit of content, from the viewpoint of the anti-flammability and weatherability that are well maintained resin-formed body, preferably 50 mass parts with Under, more preferably 30 below the mass, and further preferably 15 below the mass.
The manufacturing method > of < (methyl) acrylic resin composition
As the method for obtaining (methyl) acrylic resin composition of the invention, can enumerate aftermentioned polymerism group Close the method that object (X3) is polymerize.
As when above-mentioned polymerizable composition, polymerizable composition (X3) to be polymerize and obtain (methyl) acrylic resin composition Used radical polymerization initiator can be enumerated for example, 2,2 '-azos two (isobutyronitrile), 2,2 '-azo, two (2,4- diformazans Base valeronitrile) etc. the peroxide such as azo-compounds and benzoyl peroxide, lauroyl peroxide.It can according to need and free radical Polymerization initiator is together and with promotors such as amine, mercaptan.
Polymerization temperature when polymerizable composition, polymerizable composition (X3) is polymerize causes generally according to used free radical polymerization The type of agent and suitably set in the range of 20~150 DEG C.In addition, polymerizable composition, polymerizable composition (X3) can according to need, more It is polymerize under the conditions of the temperature in stage.
As the polymerization of polymerizable composition, polymerizable composition (X3), can enumerate for example, mass polymerization, suspension polymerization, lotion are poly- Legal and dispersion copolymerization method, wherein from the aspect of productivity, preferably mass polymerization, in mass polymerization, more preferably For cast polymerization (cast polymerization (cast polymerization)) method.
In the case where obtaining (methyl) acrylic resin composition by cast polymerization method, for example, can pass through Polymerizable composition, polymerizable composition (X3) is injected into casting mold and makes its polymerization, to obtain (methyl) acrylic resin composition.
As above-mentioned casting mold, it is, for example, possible to use the end of the SUS plate of the spatial portion between 2 SUS plates be clamped with it is soft The casting mold of the sealing material such as matter vinyl chloride resin pipe.The interval in the gap of casting mold is in a manner of obtaining the resin plate of desired thickness Carry out appropriate adjustment, it is however generally that, it is 1~30mm.
< polymerizable composition, polymerizable composition (X3) >
Polymerizable composition, polymerizable composition (X3) is an embodiment party for obtaining the raw material of (methyl) acrylic resin composition Formula is the composition containing aftermentioned monomer composition (X1), above-mentioned phosphorus flame retardant (C) and above-mentioned amphiphilic compound (E).
In addition, above-mentioned monomer composition (X1) can be in advance comprising containing the repetitive unit from (methyl) acrylate Polymer.Specifically, monomer composition (X1) can be in advance comprising containing from above-mentioned (methyl) acrylate (M) The polymer (P1) of repetitive unit.By the inclusion of above-mentioned polymer, so that polymerizable composition, polymerizable composition (X3), which becomes, has sticking liquid Body (hereinafter referred to as " paste resin "), therefore polymerization time can be shortened, it can be improved productivity.
As the method for obtaining above-mentioned paste resin, can enumerate for example, the side for making polymer be dissolved in monomer composition (X1) Method, or well known radical polymerization initiator, the method for polymerizeing part of it are added in monomer composition (X1).
In addition, in the manufacturing method of the present invention, above-mentioned polymerizable composition, polymerizable composition (X3) is preferably including above-mentioned monomer in advance In the mixture (X2) of composition (X1), above-mentioned amphiphilic compound (E) and above-mentioned polymer (P1) as needed, after It is continuous to add above-mentioned phosphorus flame retardant (C) to obtain.
In addition, containing selected from multiplet acrylic acid series copolymer particle (D1) or acrylic block copolymer (D2) At least one of in the case where impact resistance modifier (D), impact resistance modifier (D) is preferably added to said mixture (X2), The further subsequent above-mentioned phosphorus flame retardant (C) of addition, obtains above-mentioned polymerizable composition, polymerizable composition (X3).
By subsequent addition phosphorus flame retardant (C), so as to steadily manufacture (methyl) propylene with high flame retardant Sour based resin composition.The reason is not yet clear for it, thus it is speculated that this is because there is no amphipathic in above-mentioned monomer composition (X1) In the state of compound (E), if addition phosphorus flame retardant (C), phosphorus flame retardant forms agglutination particle.
In addition, above-mentioned monomer composition (X1) is set as 100 mass parts for above-mentioned polymerizable composition, polymerizable composition (X3), Can containing more than above-mentioned phosphorus flame retardant (C) 5.0 mass parts 35.0 below the mass with above-mentioned amphiphilic compound (E) 0.01 It is more than mass parts that 2.0 below the mass.In addition, in the case where polymerizable composition, polymerizable composition (X3) is the paste resin comprising polymer, As long as the total amount of above-mentioned monomer composition (X1) and above-mentioned polymer is set as 100 mass parts.
If the lower limit of the content of phosphorus flame retardant (C) is 5.0 mass parts or more, the anti-flammability of resin-formed body becomes Well.In addition, if the upper limit of the content of phosphorus flame retardant (C) is the 35.0 below the mass then heat resistance of resin-formed body Become good.
If the lower limit of the content of amphiphilic compound (E) is 0.01 mass parts or more, phosphorus flame retardant (C) is not formed Agglutination particle, the anti-flammability of resin-formed body become well, therefore preferably, more than more preferably 0.05 mass parts, further excellent It is selected as 0.1 mass parts or more.If the upper limit of the content of amphiphilic compound (E) is 2.0 below the mass resin-formed body Anti-flammability become well, therefore preferably, more preferably 0.6 below the mass, and further preferably 0.3 below the mass.
In addition, (methyl) acrylate (M) of polymerizable composition, polymerizable composition (X3), methyl methacrylate and monomer (B) contain Amount is not particularly limited, such as (methyl) acrylic acid series polymeric compounds (P) that (methyl) acrylic resin composition is included can To include 19.95 mass % of repetitive unit or more, the 84.95 mass % from methyl methacrylate relative to gross mass Below, from 3.6 mass % of repetitive unit or more, the 80.0 mass % or less of (methyl) acrylate (M) and from single 0.05 mass % of structural unit or more, the 0.40 mass % mode below of body (B) suitably determines.
As an embodiment of polymerizable composition, polymerizable composition (X3), the case where polymerizable composition, polymerizable composition (X3) is paste resin Under, the composition comprising following polymer (a) He monomer composition (X1) can be enumerated.
Polymer (a)：
Include 19.95 mass % of repetitive unit or more, the 84.95 mass % or less from methyl methacrylate, source In 3.6 mass % of repetitive unit or more, the 80.0 mass % or less of above-mentioned (methyl) acrylate (M) and from above-mentioned list 0.05 mass % of structural unit or more, the 0.40 mass % polymer below of body (B).
Monomer composition (X1)：
It include 19.95 mass % of methyl methacrylate or more, 84.95 matter relative to the gross mass of monomer composition (X1) Measure 3.6 mass % of monomer or more, the 80.0 mass % or less and above-mentioned monomer (B) of % or less, (methyl) acrylate (M) 0.05 mass % or more, 0.40 mass % monomer composition below.
By the polymerizable composition, polymerizable composition (X3) of above method acquisition compared with by the polymerizable composition, polymerizable composition of previous method acquisition, It is able to extend pot life.Specifically, can make pot life 168 hours or so, therefore have in manufacture scene, production Manage the effect become easy.In addition, at this point, the temperature for saving polymerizable composition, polymerizable composition is not particularly limited, but if saving temperature The lower limit of degree is 5 DEG C or more, then the limitation in equipment is few, therefore preferably, more preferably 10 DEG C or more.On the other hand, temperature is saved The upper limit of degree is not particularly limited, but if being 40 DEG C hereinafter, being then preferably, more from the viewpoint of the safety in preservation Preferably 30 DEG C or less.
< monomer composition (X1) >
So-called monomer composition (X1) is the composition comprising above-mentioned (methyl) acrylate (M).By the inclusion of (methyl) Acrylate (M) so that the anti-flammability of resin-formed body improves, and by the effect of above-mentioned amphiphilic species (E), can press down Phosphorus flame retardant (C) processed forms agglutination particle.
Further, it in the case where above-mentioned monomer composition (X1) includes above-mentioned (methyl) acrylate (M), may include Methyl methacrylate and above-mentioned monomer (B).
By the inclusion of methyl methacrylate, so as to keep heat resistance and the weather resistance of resin-formed body excellent, and And mechanical strength, thermal property, molding processibility are more excellent.
By the inclusion of above-mentioned monomer (B), so as to keep anti-flammability, heat resistance, mechanical property more excellent.
The content of (methyl) acrylate (M), methyl methacrylate and monomer (B) in monomer composition (X1) not by It is particularly limited to, for example, (methyl) acrylic acid series polymeric compounds (P) that (methyl) acrylic resin composition is included can be with phase Include 19.95 mass % of repetitive unit or more, the 84.95 mass % or less for deriving from methyl methacrylate for gross mass, come Derived from 3.6 mass % of repetitive unit or more, the 80.0 mass % or less of (methyl) acrylate (M) and from monomer (B) 0.05 mass % of structural unit or more, 0.40 mass % mode below suitably determines.
In addition, above-mentioned (methyl) acrylate (M), which may include side chain, has fragrance in above-mentioned monomer composition (X1) 10.0 mass % of methacrylate (M1) or more, the 79.5 mass % of the alicyclic type hydrocarbon of race's alkyl or carbon atom number 3~20 with Under and side chain have aromatic hydrocarbyl or carbon atom number 3~20 alicyclic type hydrocarbon 0.50 mass % of acrylate (M2) The above 20.0 mass % or less.
Methacrylate (M1) and acrylate (M2) and phosphorus flame retardant (C) interact, and have and synergistically improve The effect of anti-flammability improvement effect possessed by phosphorus flame retardant (C), therefore can be improved the anti-flammability of resin-formed body.
In addition, by the inclusion of acrylate (M2), thus in (methyl) acrylic resin composition after polymerization not Reaction monomers are reduced, therefore the weatherability of the resin-formed body obtained becomes good.
As specific methacrylate (M1) and acrylate (M2), above compound can be enumerated.
From the viewpoint of the improvement effect of anti-flammability and flame resistance is excellent, it can make in above-mentioned methacrylate (M1) With selected from least one of cyclohexyl methacrylate and isobornyl methacrylate.
From the viewpoint of the improvement effect of anti-flammability and weatherability is excellent, above-mentioned (methyl) acrylate (M2) passes through packet Containing at least one of cyclohexyl acrylate and isobornyl acrylate (hereinafter, " monomer (m2) ") is selected from, so as to mention The molding weatherability of high resin, anti-flammability.The content of monomer (m2) can be set to 1.0 mass parts or more 4.99 below the mass.
By the inclusion of monomer (m2), so as to be further reduced in (methyl) acrylic resin composition after polymerization Unreacted monomer, the weatherability of resin forming becomes better.Further, monomer (m2) and phosphorus flame retardant interact, Have the effect of synergistically improving anti-flammability improvement effect possessed by phosphorus flame retardant, therefore can be improved resin-formed body Anti-flammability.
The lower limit of the content of monomer (m2) is not particularly limited, by relative to above-mentioned (methyl) acrylic acid series polymeric compounds (P) 100 mass parts are set as 1.0 mass % or more, so as to keep anti-flammability and the weatherability of resin-formed body better, because This is preferred, more preferably 2.0 mass % or more.On the other hand, the upper limit of content is not particularly limited, if content is 4.99 matter % is measured hereinafter, can then further increase the heat resistance of resin-formed body, therefore preferably, more preferably 4.0 mass % or less.On Stating upper limit value and lower limit value can arbitrarily combine.
As above-mentioned monomer composition, can enumerate for example, further dissolution includes to come in above-mentioned monomer composition (X1) Derived from the monomer composition of the polymer (P1) of the repetitive unit of above-mentioned (methyl) acrylate (M), or make above-mentioned monomer group Monomer composition obtained by the polymerization of object (X1) a part is closed, the sticking liquid (hereinafter referred to as " paste resin ") of tool can be enumerated The monomer composition of form.
As an embodiment of monomer composition (X1), for example, being only by monomer shape at polymerizable composition, polymerizable composition (X3) At monomer composition (X1) in the case where, the gross mass relative to monomer composition (X1) can be enumerated, include methacrylic acid The 15.0 mass % of monomer or more 80.0 of 19.95 mass % of methyl esters or more, 84.95 mass % or less, (methyl) acrylate (M) 0.40 mass % composition below of quality % or less and 0.05 mass % of above-mentioned monomer (B) or more.
Alternatively, the another embodiment as monomer composition (X1), can enumerate for example, relative to monomer composition (X1) gross mass includes 19.95 mass % of methyl methacrylate or more, 79.1 mass % or less, (methyl) acrylate (M) 0.40 mass % of 20.5 mass % of monomer or more 80.0 mass % or less and 0.05 mass % of above-mentioned monomer (B) or more Composition below.
It is the list comprising having 2 or more ethylenic unsaturated bonds in molecule that the present invention, which can enumerate above-mentioned monomer composition (X1), The manufacturing method of 0.05 mass % of body (B) or more, 0.40 mass % (methyl) acrylic resin composition below.
< resin-formed body >
Resin-formed body is manufactured by using above-mentioned (methyl) acrylic resin composition, so as to steadily obtain There must be the resin-formed body of high flame retardant.
The manufacturing method > of < resin-formed body
The manufacturing method of resin-formed body is not particularly limited, and can enumerate for example following 2 methods.
(1) above-mentioned polymerizable composition, polymerizable composition (X3) is injected into casting mold, after polymerizeing it using well known cast polymerization method, from casting Type takes out the method for obtaining resin-formed body.
(2) particle of (methyl) acrylic resin composition of the invention is used into the public affairs such as extrusion molding or injection moulding The melt molding method known is come the method that obtains resin-formed body.
< laminated resin body >
Laminated resin body of the invention is using above-mentioned resin-formed body as resin base material (A), on its at least one surface The laminated resin body for having the aftermentioned sheet for solidifying envelope (F).Resin base material (A) is for assigning high resistant to laminated resin body The layer of combustion property, heat resistance, weatherability, solidifying envelope (F) is the layer for assigning high marresistance to laminated resin body.
By the schematic diagram of laminated resin body of the invention in Fig. 2, Fig. 3.Fig. 2 is in a face of resin base material (A) Skeleton diagram with the laminated resin body for solidifying envelope (F).Fig. 3 is to have to solidify envelope (F) on the two sides of resin base material (A) The skeleton diagram of laminated resin body.
< solidifies envelope (F) >
In laminated resin body of the invention, above-mentioned solidification envelope (F) is by having 3 or more (methyl) containing aftermentioned The polyfunctional monomer (F1) (hreinafter referred to as " polyfunctional monomer (F1) " of acryloyl group.), aftermentioned there are 2 (methyl) third The polyfunctional monomer (F2) (hreinafter referred to as " polyfunctional monomer (F2) " of enoyl-.) active energy ray-curable combination Object (f) (hereinafter referred to as " solidification compound (f) ".) solidfied material formed solidification envelope.
In addition, what above-mentioned solidification envelope (F) was included derives from polyfunctional monomer (F1) in laminated resin body of the invention Repetitive unit and be not particularly limited from the content of repetitive unit of polyfunctional monomer (F2), can be made will solidify quilt The total weight of film (F) is set as 100 mass %, contains 50 mass % of repetitive unit or more, 80 matter from polyfunctional monomer (F1) Measure the resin combination of % and 20 mass % of repetitive unit or more, the 50 mass % from polyfunctional monomer (F2).
Become well from the marresistance for solidifying envelope (F), derives from the repetitive unit of polyfunctional monomer (F1) The lower limit of content is preferably 50 mass % or more, more preferably 60 mass % or more.It is small from the cure shrinkage for solidifying envelope (F) Ground is not likely to produce crack, also, is formed with and solidifies the laminated resin plate of envelope (F) and be not likely to produce from the perspective of warpage, source In the upper limit of the content of the repetitive unit of polyfunctional monomer (F1) be preferably 80 mass % hereinafter, more preferably 70 mass % with Under.Above-mentioned upper limit value and lower limit value can be combined arbitrarily.
From the viewpoint of the marresistance for solidifying envelope becomes good, the repetitive unit of polyfunctional monomer (F2) is derived from The upper limit of content be preferably 50 mass % hereinafter, more preferably 40 mass % or less.It is received from solidification when solidifying composition Shrinkage is small, and solidification envelope (F) is not likely to produce crack, and resin base material (A) and the adaptation for solidifying envelope (F) become good viewpoint It sets out, the lower limit from the content of the repetitive unit of polyfunctional monomer (F2) is preferably 20 mass % or more, more preferably 30% mass % or more.Above-mentioned upper limit value and lower limit value can be combined arbitrarily.
< polyfunctional monomer (F1) >
In laminated resin body of the invention, by containing the weight from polyfunctional monomer (F1) in solidifying envelope (F) Multiple unit, so as to obtain the laminated resin body with high marresistance.
As specific polyfunctional monomer (F1), following (1)~(5) can be enumerated.They can be used alone, can also To be used in combination of two or more.
(1) carboxylate obtained by (methyl) acrylic acid of polyalcohol and 3 moles or more；
Specifically, trimethylolpropane tris (methyl) acrylate, three ((methyl) acryloyl-oxyethyls) can be enumerated Isocyanuric acid ester, pentaerythrite three (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta 4 Compound well known to alcohol six (methyl) acrylate etc..
(2) being obtained by polyalcohol, polybasic carboxylic acid or its acid anhydride and (methyl) acrylic acid, there are 3 or more in 1 molecule The carboxylate of the line style of (methyl) acryloxy；
Specifically, can enumerate malonic acid/trimethylolethane/(methyl) acrylic acid, malonic acid/trimethylolpropane/ (methyl) acrylic acid, malonic acid/glycerol/(methyl) acrylic acid, malonic acid/pentaerythrite/(methyl) acrylic acid, succinic acid/tri- Hydroxymethyl ethane/(methyl) acrylic acid, succinic acid/trimethylolpropane/(methyl) acrylic acid, succinic acid/glycerol/(methyl) third Compound well known to olefin(e) acid, succinic acid/pentaerythrite/(methyl) acrylic acid etc..
(3) to the acrylic monomer of the polyisocyanates and active hydrogen that obtain by trimerizing, make every 1 mole Carbamate obtained by polyisocyanates is reacted with 3 moles or more of acrylic monomer (methyl) acrylate；
As the polyisocyanates obtained by trimerizing, such as trimethylolpropane toluene diisocyanate can be enumerated Compound well known to ester, hexamethylene diisocyanate, toluene di-isocyanate(TDI) etc..
As the acrylic monomer of active hydrogen, such as (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) can be enumerated Known in acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxy-3-methoxy propyl ester, N- methylol (methyl) acrylamide etc. Compound.
(4) poly- [(methyl) acryloxy ethylidene] isocyanuric acid ester；
Specifically, two (methyl) acrylate or three (methyl) propylene of three (2- hydroxyethyl) isocyanuric acids can be enumerated Acid esters etc..
(5) epoxy polyacrylate well known to
(6) carbamate polyacrylate well known to
Wherein, pentaerythrite three (methyl) acrylate documented by above-mentioned (1), three ((methyl) acryloyl-oxyethyls) Isocyanuric acid ester, trimethylolpropane tris (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, Ji Wusi Alcohol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate,
The condensation product of polyalcohol documented by above-mentioned (2), polybasic carboxylic acid or its acid anhydride and (methyl) acrylic acid is due to curability With the excellent scratch resistance obtained for solidifying envelope, therefore preferably.
< polyfunctional monomer (F2) >
In laminated resin body of the invention, by making to solidify envelope (F) containing the repetition from polyfunctional monomer (F2) Unit so that the cure shrinkage for solidifying envelope (F) becomes smaller, therefore is not likely to produce crack, is further able to obtain solidification envelope (F) with the good laminated resin body of adaptation of resin base material (A).
As specific polyfunctional monomer (F2), such as ethylene glycol two (methyl) acrylate, dicyclopentenyl can be enumerated The polyethylene glycol such as two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate Two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, two (first of ethylene oxide denatured trimethylolpropane Base) acrylate, tripropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, two (first of 1,4- butanediol Base) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, two (first of polyester Base) compound well known to acrylate etc..
These compounds can be used one kind or two or more be applied in combination.Wherein, 1,6- hexylene glycol two (methyl) acrylic acid Ester, (methyl) acrylate of 1,9- nonanediol two solidify the excellent with the adaptation and marresistance of substrate of envelope due to resulting It is different, therefore more preferably.
< solidification compound (f) >
Above-mentioned solidification envelope (F) can make the solidification containing above-mentioned polyfunctional monomer (F1) and above-mentioned polyfunctional monomer (F2) Property composition (f) solidified using well known method and obtain.
As above-mentioned solidification compound (f), it can be used and containing above-mentioned polyfunctional monomer (F1) 50 mass % or more 80 mass % or less and above-mentioned polyfunctional monomer (F2) 20 mass % or more, 50 mass % above-mentioned solidification compound (f) below In, the solidification compound of the aftermentioned Photoepolymerizationinitiater initiater of predetermined amount is only added as needed.
Become smaller from the cure shrinkage for solidifying envelope (F), be not likely to produce crack, there is the stacking for foring and solidifying envelope (F) Resin plate is not likely to produce from the perspective of the tendency of warpage, the upper limit of the content of polyfunctional monomer (F1) be preferably 80 mass % with Under, more preferably 70 mass % or less.From the viewpoint of the marresistance for solidifying envelope (F) becomes good, polyfunctional monomer (F1) lower limit of content is preferably 50 mass % or more, more preferably 60 mass % or more.Above-mentioned upper limit value and lower limit value can Arbitrarily to combine.
From the viewpoint of the marresistance for solidifying envelope becomes good, the upper limit of the content of polyfunctional monomer (F2) is preferred For 50 mass % hereinafter, more preferably 40 mass % or less.It is small from cure shrinkage when solidifying solidification compound, solidification Envelope (F) is not likely to produce from the perspective of crack, and the lower limit of the content of polyfunctional monomer (F1) is preferably 20 mass % or more, more Preferably 30 mass % or more.Above-mentioned upper limit value and lower limit value can be combined arbitrarily.
< Photoepolymerizationinitiater initiater >
As above-mentioned Photoepolymerizationinitiater initiater, well known compound can be used.Specifically, benzoin can be enumerated and its spread out Biology, benzophenone and its derivative, acetophenone and its derivative, glyoxalic acid alkylbenzene base ester, 2- hydroxy-2-methyl -1- benzene Sulphur compounds such as carbonyls, the tetramethylthiuram monosulfides such as base propane -1- ketone etc..These Photoepolymerizationinitiater initiaters can be single Solely using one kind, also two or more kinds may be used.
The additive amount of Photoepolymerizationinitiater initiater is not particularly limited, can be relative to above-mentioned 100 mass of solidification compound (f) Part, add 0.5 mass parts of Photoepolymerizationinitiater initiater or more 6.0 below the mass.
Other additives of < >
In above-mentioned solidification compound (f), it can according to need various additives used in addition all the time.Specifically For, surfactant, levelling agent, dyestuff, pigment, antioxidant, ultraviolet absorbing agent, stabilizer, fire retardant, increasing can be enumerated Mould agent etc., the monofunctional monomer for assigning function.
The additive amount of additive is suitably determined in the range of not damaging the physical property of above-mentioned solidification envelope (F) obtained, 10 can be set as below the mass relative to above-mentioned 100 mass parts of solidification compound (f).
The thickness G T.GT.GT of < laminated resin body
The integral thickness of laminated resin body of the invention is not particularly limited, from the mouldability and anti-flammability of laminated resin body From the perspective of excellent, preferably 1mm or more 30mm is hereinafter, more preferably 3mm or more 10mm or less.In addition, so-called resin layer The whole thickness of stack refers to the thickness of resin base material (A) and solidifies the total of the thickness of envelope (F).
The film thickness of the solidification envelope (F) of laminated resin body of the invention is not particularly limited, from the anti-scratch of laminated resin body From the perspective of wound property and excellent in flame retardance, preferably 0.1 μm or more 100 μm hereinafter, more preferably 3 μm or more 30 μm or less.
The manufacturing method > of < laminated resin body
In the present invention, the manufacturing method of laminated resin body is not particularly limited, can be used with batch-type, continous way into The manufacturing method of capable well known laminated resin body.
As continuous manufacturing method, the resin base material (A) using well known continuous casting process manufacture sheet can be enumerated, Then, above-mentioned solidification envelope (F) is laminated continuously at least one surface of above-mentioned resin base material (A) in the production line, makes The method of molding resins laminated body.From the viewpoint of the productivity of laminated resin body is excellent, preferably continuous casting process.
As the manufacturing method of batch-type, for example following 2 kinds of methods can be enumerated.
Method (1)：It is formed at least one surface of resin base material (A) comprising above-mentioned polyfunctional monomer (F1) and above-mentioned more After the layer of the solidification compound (f) of functional monomer (F2), make its solidification, forms the method for solidifying the layer of envelope (F).
Method (2)：Make the solidification compound (f) comprising above-mentioned polyfunctional monomer (F1) and above-mentioned polyfunctional monomer (F2) Solidification is formed after solidification envelope (F), is formed the layer of resin base material (A) on the surface of above-mentioned solidification envelope (F) and is obtained resin The method of laminated body.
< method (1) >
The above method (1) of manufacturing method as batch-type, can specifically enumerate following methods.
Firstly, injecting raw material of the above-mentioned polymerizable composition, polymerizable composition (X3) as resin base material (A) in casting mold, passing through casting Polymerization solidifies above-mentioned polymerizable composition, polymerizable composition (X3), removes from casting mold, obtains resin base material (A).Then, at resin base material (A) Surface coating contain above-mentioned polyfunctional monomer (F1) and above-mentioned polyfunctional monomer (F2) solidification compound (f), by surface It is covered with resin film.Then, by irradiating active energy beam across resin film to above-mentioned solidification compound (f), to make Above-mentioned solidification compound (f) solidification, obtains solidification envelope (F).Then, resin film is removed, laminated resin body is obtained.
As the type of casting mold, the model such as mold, piece can be enumerated.Casting mold makes 2 models usually to be formed with solidification The mode that the face of envelope becomes inside opposed makes.In above-mentioned model, be formed with solidify envelope face preferably have it is smooth Surface.As the material of casting mold, can enumerate such as stainless steel, glass and resin.Casting mold can be 2 models for making same material Opposed casting mold is also possible to the casting mold for keeping 2 models of unlike material opposed.
In the casting mold for keeping 2 models opposed, pad is arranged in the peripheral part by being formed by spatial portion between these models Circle is to be sealed, to make the stacking casting mold that inside has a constant volume.
As resin film, can enumerate for example, polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film and polyvinylidene fluoride (PVDF) film.Wherein, from cost and the curability aspect for solidifying envelope, preferably PET Film.As the thickness of resin film, preferably 8~125 μm.
As active energy beam, such as electron ray, ultraviolet light and luminous ray can be enumerated, from installation cost, production From the perspective of rate, preferably ultraviolet light.The light quantity of active energy beam is not particularly limited, and accumulative light quantity is preferably 5~ 2000mJ/cm2。
In addition to this, the particle using above-mentioned (methyl) acrylic resin composition can be enumerated, extrusion molding, note are passed through It penetrates after the resin base materials (A) of the melt moldings method to obtain sheet such as molding, on the surface of above-mentioned resin base material (A), uses Well known infusion process forms the method for solidifying the layer of envelope (F).
< method (2) >
As the manufacturing method (2) of above-mentioned batch-type, following methods can be specifically enumerated.
Firstly, in solidification of the inner face coating containing above-mentioned polyfunctional monomer (F1) and above-mentioned polyfunctional monomer (F2) of model Property composition (f), surface is covered with resin film.Then, solidification compound (f) irradiation active-energy is penetrated across resin film Line obtains solidification envelope (F) so that above-mentioned solidification compound (f) be made to solidify.Then, resin film is removed, is obtained in model Interior surface layers are laminated with the stacking casting mold for solidifying envelope (F).In stacking casting mold obtained, above-mentioned polymerizable composition, polymerizable composition is injected (X3) raw material as resin base material (A) solidifies the polymerizable composition, polymerizable composition by cast polymerization, is laminated with admittedly to obtain Change the resin base material (A) of envelope (F).Then, it is removed from casting mold, obtains laminated resin body.
As casting mold, casting mold same as above-mentioned casting mold can be used.
As resin film, film same as above-mentioned resin film can be used.
As active energy beam, energy-ray same as above-mentioned active energy beam can be used, as using The curing method of active energy beam can use method similar to the above and be solidified.
Embodiment
Hereinafter, explaining the present invention in detail by embodiment.Hereinafter, " part " and " % " respectively indicate " mass parts " and " quality % ".In addition, the various evaluations in embodiment are implemented by following methods.
In addition, the abbreviation of compound used in embodiment and comparative example is as follows.
MMA：Methyl methacrylate
IBXMA：Isobornyl methacrylate
IBXA：Isobornyl acrylate
TBMA：Tert-butyl Methacrylate
BA：N-butyl acrylate
EDMA：Ethylene glycol dimethacrylate
CR-570：Condensed phosphoric acid esters containing halogen (trade name, big eight chemical industry (strain) system)
CR-504L：Condensed phosphoric acid esters containing halogen (trade name, big eight chemical industry (strain) system)
SDS：Dioctyl sodium sulphosuccinate
SS：Odium stearate
SLS：NaLS
PEH：Phosphoric acid 2- ethylhexyl
HPP：The tertiary own ester of peroxidating neopentanoic acid
CHMA：Cyclohexyl methacrylate
DCPMA：Two ring pentyl ester of methacrylic acid
ADMA：Adamantylmethacrylate
p-PPMA：Methacrylic acid-is to biphenyl ester
PhMA：Phenyl methacrylate
MA：Methyl acrylate
ST：Styrene
AMA：Allyl methacrylate
BDMA：1,3 butylene glycol dimethylacrylate
DBP：Di-t-butyl peroxide
n-OM：N octylmercaptan
Emulsifier (1)：Single (ethylene nonyl phenyl ether) phosphatase 24 0% and two (ethylene nonyl phenyl ether) phosphoric acid The sodium hydroxide part corrective of 60% mixture
SFS：Rongalite
CHP：Cumyl hydroperoxide
Rubber A：Multiplet acrylic acid series copolymer particle (Production Example 1)
Rubber B：Multiplet acrylic acid series copolymer particle (Production Example 2)
Block polymer：Commercially available acrylic block copolymer (trade name：KURARITY, Kuraray Co., Ltd. System)
Polyacrylate 1：Dipentaerythritol hexaacrylate (60 mass % or more, 70 mass % or less) and two seasons penta 4 The mixture of five acrylate of alcohol (30 mass % or more, 40 mass % or less).
Diacrylate 1：1,6 hexanediol diacrylate
BEE：Benzoin ethyl ether
< evaluation method >
Evaluation in embodiment and comparative example is implemented by the following method.
(1) anti-flammability (JIS)
Test film (the length 127mm of resin-formed body is made according to the fire resistance test A method of JIS K 6911-1995 × width 12.7mm), measurement required time (self-extinguishing time) until test film self-extinguishment.
A：The self-extinguishing time of test film was less than 1 minute.
B：The self-extinguishing time of test film was 1 minute more than and less than 2 minutes.
C：The self-extinguishing time of test film was 2 minutes more than and less than 3 minutes.
D：The self-extinguishing time of test film is 3 minutes or more.
E：The non-self-extinguishment of test film.
(2) anti-flammability (UL94)
The test film (length 125mm × width 13.0mm) of resin-formed body is evaluated according to UL94 testing vertical flammability method Anti-flammability.The judgement of anti-flammability is carried out based on benchmark shown in following table 1.
[table 1]
(3) heat resistance
The test film (length 127mm × width 12.7mm) of laminated resin body, measurement examination are made according to JIS K 7191 The loading flexure temperature (hereinafter, being expressed as " HDT ") (DEG C) of piece is tested to evaluate heat resistance.
(4) dispersion particle diameter
It is right using optical microscopy with 1000 times of observation resin-formed bodies of multiplying power or (methyl) acrylic resin composition In the dispersed particle or agglutination particle of any 20 phosphorus flame retardants (C) observed, measure dispersed particle primary particle size or The aggregate particle size of agglutination particle, using its average value as dispersion particle diameter." N.D. " is set as when not observing dispersed particle.In addition, The offspring that dispersed particle (primary particle) is contacted and formed is set as agglutination particle.
(5) half width at the peak of decomposition product
As gas analysis measurement device occurs, use gaschromatographic mass spectrometric analysis meter (as the Agilent of gas-chromatography Corporation, product name：HP6890, as the Frontier-lab corporation of heating furnace (pyrolysis furnace), product name：PY2020D makees For the Hewlett-Packard corporation of mass spectral analysis meter, product name：HP-5973, pyrolysis furnace and mass spectral analysis meter use non-live Property capillary (Ultra Alloy DTM 2.5m, 0.15mm directly link), measure (methyl) acrylic resin composition institute The half width at the peak of the decomposition product for the repetitive unit from (methyl) acrylate (M) for including.
(methyl) acrylic resin composition 2mg is set in gas analysis measurement device occurs, under helium atmosphere (flow velocity 20ml/ minutes), with 10 DEG C/min of generations to heat up from temperature 60 C up to 550 DEG C, for decomposition product of heating rate Gas is analyzed by mass spectrometry, and achieves temperature-chromatographic curve.It, will be as (methyl) acrylate in temperature-chromatographic curve (M) peak observed when describing chromatogram in the characteristic mass-charge ratio (m/z) of generation gas is used as from (first Base) acrylate (M) repetitive unit generation gas peak, the half from the baseline at peak up to the height of summit will be located at Peak width is set as the half width at peak.In addition, even if being found out in the case where peak shape is not normal distribution also by the above method Half width.In addition, the decomposition product of the generation gas of (methyl) acrylate (M), phosphorus flame retardant (C) is most characteristic Mass-charge ratio (m/z) can be known respectively by being measured using individual sample.
The mass-charge ratio (m/z) of compound used in the present embodiment and comparative example described below.
MMA：M/z=100, IBXMA：M/z=93, CHMA：M/z=82, DCPMA：M/z=66, ADMA：M/z=135, TBMA：M/z=56, p-PPMA：M/z=170, PhMMA：M/z=94, CR570：M/z=76, CR504L：M/z=125, D1500：M/z=211, D880：M/z=123.
(6) the generation temperature of decomposition product
As gas analysis measurement device occurs, use gaschromatographic mass spectrometric analysis meter (as the Agilent of gas-chromatography Corporation, product name：HP6890, as the Frontier-lab corporation of heating furnace (pyrolysis furnace), product name：PY2020D makees For the Hewlett-Packard corporation of mass spectral analysis meter, product name：HP-5973, as heating furnace (pyrolysis furnace) Frontier-lab corporation, product name：PY2020D, as the Hewlett-Packard corporation of mass spectral analysis meter, product Name：(Ultra Alloy DTM 2.5m, 0.15mm are direct using nonactive capillary for HP-5973, pyrolysis furnace and mass spectral analysis meter Connection), the repetitive unit from (methyl) acrylate (M) that measurement (methyl) acrylic resin composition is included The generation temperature Tm (DEG C) of decomposition product, from methyl methacrylate repetitive unit decomposition product generation temperature Ta The generation temperature Tc (DEG C) of the decomposition product of (DEG C) and above-mentioned phosphorus flame retardant (C).
(methyl) acrylic resin composition 2mg is set in gas analysis measurement device occurs, under helium atmosphere (flow velocity 20ml/ minutes), with 10 DEG C/min of generations to heat up from temperature 60 C up to 550 DEG C, for decomposition product of heating rate Gas is analyzed by mass spectrometry, and achieves temperature-chromatographic curve.It, will be as (methyl) acrylate in temperature-chromatographic curve (M) the generation gas of decomposition product and observed by when describing chromatogram in most characteristic mass-charge ratio (m/z) Peak as from (methyl) acrylate (M) repetitive unit decomposition product generation gas peak, methyl will be used as The peak observed when describing chromatogram in the characteristic mass number of the generation gas of methyl acrylate is used as from methyl-prop The peak of the generation gas of the decomposition product of the repetitive unit of e pioic acid methyl ester, furthermore will be as the decomposition product of phosphorus flame retardant (C) Generation gas characteristic mass number in the decomposition product of the peak that is observed as phosphorus flame retardant (C) when describing chromatogram Generation gas peak, using the highest point at temperature-chromatographic curve peak as the generation temperature of decomposition product.
In addition, the most characteristic of the decomposition product of the generation gas of (methyl) acrylate (M), phosphorus flame retardant (C) Mass-charge ratio (m/z) can be known respectively by being measured using individual sample.
Sample is to cut 2mg etc. from resin combination, for measurement.At this point, the size of with good grounds sample and resolution characteristic Changed worry, therefore become 2mg by 1~3.
(7) charpy impact intensity
According to JIS K7111-1/fU, non-notch charpy impact intensity is measured.
(8) weatherability
According to JIS K7350-4, sunlight weather resistance test case (condition is utilized：63 DEG C, 50%, the water spray time 12 minutes/60 Minute) exposure test in 1000 hours, the yellow colour index (Δ YI) of measurement test front and back are carried out to resin-formed body.
(9) surface hardness
According to JIS K5600-5-4, the pencil hardness of laminated resin body is measured, evaluates surface hardness.
(10) measurement of plate thickness
The thickness of laminated resin body is measured using slide calliper rule.
(11) measurement of film thickness
By laminated resin body on the direction parallel with thickness direction, cut off using cutting machines such as amputating saws.Then, make It is ground with cut section of the end face mirror surface finishing machine to the laminated resin body after cutting.It is ground using digital micro-analysis sem observation Section afterwards, to measure film thickness.
(12) weight average molecular weight (Mw)
Use the weight average molecular weight of gel permeation chromatography (GPC) measurement phosphorus flame retardant (C).Tetrahydrofuran (THF, With Wako Pure Chemical Industries corporation, reagent is superfine) in so that the mode of concentration of the phosphorus flame retardant (C) as 2mg/mL carry out it is molten Solution, using the solution of acquisition as the sample of GPC measurement.GPC measurement is in high performance liquid chromatography measurement device (Tosoh (strain) System, device name：HLC-8320 type) in, guard column (trade name will be connected with：TSK-guardcolumn SUPERH-L, Tosoh (strain) corporation) splitter (each name of an article：SUPER H4000,6.0mm φ × 150mm, Tosoh (strain) corporation) and splitter (trade name：SUPER H2000,6.0mm φ × 150mm, Tosoh (strain) corporation) to use, detector is rolled over using differential for connection Penetrate meter.Using separate 40 DEG C of column temperature, as the THF of mobile phase, the flow 0.6ml/min of mobile phase, 10 μ l of sample injection volume into Row measurement.Use 10 kinds of polystyrene (Mw5,970 ,~6,770,000), Irganox1010 (Mw1178) known to molecular weight With 2,2 '-di-2-ethylhexylphosphine oxides (6- Butylated Hydroxytoluene) (Mw340) make calibration curve (3 power function), find out weight average molecular weight (Mw)。
(13) measurement of the relaxation spectrum carried out using solid NMR
Resin-formed body or (methyl) acrylic resin composition are crushed or cut off, the small of 5mm square or so is obtained Piece.Then, using Freezing smashing device (device name：SPEX9750FREEZER/MILL, SPEX CertiPrep Ltd corporation, 10cps is carried out 2 minutes × 2 circulations by condition), by small pieces 2.5g Freezing smashing obtained, obtain powdered samples.By institute The powdered samples of acquisition are filled into solid NMR sample cell (φ 7mm, internal diameter φ 6mm), are measured as solid NMR Use sample.Then, using solid NMR measurement device, cross polarization method is locked by proton spin, changes spin lock time, measurement13C core and31P core spectrum.
The details of determination condition is as follows.
Solid NMR measurement device：AVANCEII 300 (Bruker BioSpin corporation)
Measuring temperature：Room temperature (22 DEG C)
Observing nuclear：13C (observing frequency 75.4MHz)
31P (observing frequency 121MHz)
Time of contact：2000μs
Pulse train：Recorded in Fig. 1
Sample rotation speed：6kHz
Repetition time：4sec
Cumulative number：512 times
The spin lock time：16,20,25,30msec
13The benchmark of C core spectrum is that the carbonyl peak of glycine is set as 176.03ppm.
31P core spectrum is that the peak of maximum intensity is set as 0ppm.
Using spin lock cross polarization method (CP method), with scheduled spin lock time τ (unit：Msec it) carries out13C core spectrum With31The measurement of P core spectrum.Spectrum corresponding to carbon with the carbonyl of acrylic resin composition (peak) is set as13C core spectrum - 180ppm~-160ppm, spectrum (peak) corresponding to the phosphorus atoms with phosphorus flame retardant (C) is set as31- the 40 of P core spectrum~ 40ppm, measures following MC (τ) and following MP (τ), and value D is calculated by following formula (a)1(%).
D1(%)=| MC (τ)-MP (τ) |/MC (τ) × 100 (a)
MC(τ)：The average value of (A) and (B) as shown below
When (A) by spin lock time τ sec13The carbon with carbonyl that 160ppm~180ppm of C nuclear ralaxation spectrum is observed When the area of corresponding spectrum is divided by 10 μ sec of spin lock time13160ppm~180ppm of C nuclear ralaxation spectrum is observed The carbon with carbonyl corresponding to spectrum the obtained value of area.
When (B) by spin lock time τ sec13The carbon with methylene that 30ppm~65ppm of C nuclear ralaxation spectrum is observed When the area of corresponding spectrum is divided by 10 μ sec of spin lock time13What 30ppm~65ppm of C nuclear ralaxation spectrum was observed The value that the area of spectrum corresponding to carbon with methylene obtains.
MP(τ)：When by spin lock time τ sec31- 40~40ppm of P nuclear ralaxation spectrum is observed and phosphorous flame-retardant When the area of spectrum corresponding to the phosphorus atoms of agent (C) is divided by 10 μ sec of spin lock time31- 40~40ppm institute of P core spectrum The value that the area of spectrum corresponding to the phosphorus atoms with phosphorus flame retardant (C) observed obtains.
[embodiment 1]
(1) manufacture of paste resin (A1)
In the reactor (polymeric kettle) for having cooling tube, thermometer and blender, investment by MMA68 mass parts, The monomer composition that IBXMA20 mass parts, IBXA3 mass parts, TBMA8 mass parts, BA1 mass parts are constituted.By above-mentioned monomer group It closes object and is maintained at room temperature, after being stirred while being bubbled with nitrogen, heated up while stirring until temperature 60 C.It connects , for above-mentioned 100 mass parts of monomer composition, add 2,2 '-azo, two (2, the 4- diformazans as radical polymerization initiator Base valeronitrile) 0.1 mass parts, above-mentioned monomer composition are heated up while stirring until being kept for 13 points after 100 DEG C of temperature Clock.Then, carry out cooling until the interior temperature of reactor is obtained as room temperature by 30 mass % of polymer and monomer composition 70 Quality % (detail is MMA68 mass %, IBXMA20 mass %, IBXA3 mass %, TBMA8 mass %, BA1 mass %) is constituted Paste resin (A1).
(2) cast polymerization
Relative to 100 mass parts of above-mentioned paste resin (A1), 0.12 mass parts of EDMA as monomer (B) are added, in room temperature It is lower to be made it dissolve while stirring 10 minutes, obtain monomer composition (X1).Further at above-mentioned monomer composition (X1) SDS (dioctyl sodium sulphosuccinate) 0.2 mass parts of the middle addition as amphiphilic compound (E), are stirred on one side at room temperature It makes it dissolve on one side within 10 minutes, obtains mixture (X2).Then, CR- of 10.5 mass parts of addition as phosphorus flame retardant (C) 570, as tertiary own 0.3 mass parts of ester of the peroxidating neopentanoic acid of polymerization initiator, dissolved product is set as polymerism combination Object (X3).
Peripheral part between 2 SUS plates arranged opposite, so that the gapping interval of 2 SUS plates becomes the side of 4.1mm Vinyl chloride resin washer is arranged in formula, produces casting mold.It modulates above-mentioned polymerizable composition, polymerizable composition (X3) and stands 1 hour later, then, In above-mentioned casting mold, inject polymerizable composition, polymerizable composition (X3), after being fully sealed using vinyl chloride resin washer, heating direct immediately It to 82 DEG C, is kept for 30 minutes, then heating is kept for 30 minutes up to 130 DEG C, polymerize polymerizable composition, polymerizable composition (X3).That is, from adding The time for adding phosphorus flame retardant (C) to rise until starting polymerization is 1 hour.Then, cooling after room temperature, SUS plate is removed, Obtain the resin-formed body of the plate of thickness 3mm.
The examination of the test film, Evaluation of Heat Tolerance of anti-flammability evaluation is cut out from the resin-formed body obtained using cutting machine Test piece.It is cut with end face of the milling machine to the test film after cutting out.By the resin-formed body of acquisition evaluation result is shown in table 2, in 4.Fire resistance test A method (hreinafter referred to as " anti-flammability of the anti-flammability of resin-formed body in JIS K 6911-1995 (JIS) " self-extinguishing time is 1.0 minutes in).In addition, being observed using optical microscopy resin-formed body obtained, tie Fruit does not observe the agglutination particle more than 0.1 μm.In addition, value D1It is 2.7%, value D2It is 5.1%.
[embodiment 2,3]
By the time until polymerizeing until since addition is as the CR-570 of phosphorus flame retardant (C) as recorded in table 2 As changed, in addition to this, resin-formed body is obtained using method similarly to Example 1.It will be obtained Resin-formed body evaluation result is shown in table in 4.
[embodiment 4~6]
By the additive amount of phosphorus flame retardant (C), and since addition is as the CR-570 of phosphorus flame retardant (C) up to Time until polymerization is changed as documented by table 2, in addition to this, is obtained using method similarly to Example 1 Obtained resin-formed body.By resin-formed body obtained evaluation result is shown in table in 4.
[embodiment 7,8]
The additive amount of amphiphilic compound (E) is changed as documented by table 2,4, in addition to this, is used Method similarly to Example 1 obtains resin-formed body.By resin-formed body obtained evaluation result is shown in table in 4.
[embodiment 9,10]
0.2 mass parts of SS (odium stearate) as amphiphilic compound (E) are added, by the addition of phosphorus flame retardant (C) Amount changed as documented by table 2,4, in addition to this, using method similarly to Example 1 obtain resin at Type body.By resin-formed body obtained evaluation result is shown in table in 4.
[embodiment 11,12]
0.2 mass parts of SLS (NaLS) as amphiphilic compound (E) are added, by phosphorus flame retardant (C) Additive amount is changed as documented by table 2,4, in addition to this, using method tree similarly to Example 1 Rouge formed body.By resin-formed body obtained evaluation result is shown in table in 4.
[embodiment 13,14]
PEH (phosphoric acid 2- ethylhexyl) 0.05 mass parts as amphiphilic compound (E) are added, by phosphorus flame retardant (C) since additive amount and the time adding phosphorus flame retardant (C) until until polymerization carry out as table 2 is recorded Change, in addition to this, obtains resin-formed body using method similarly to Example 1.By resin-formed body obtained Evaluation result is shown in table in 4.
[embodiment 15]
Used as the CR-504L of phosphorus flame retardant (C), additive amount is changed as documented by table 2,4, In addition to this, resin-formed body is obtained using method similarly to Example 1.By the evaluation knot of resin-formed body obtained Fruit is shown in Table 4.
[comparative example 1]
Using the paste resin (A) that is made by embodiment 1, when carrying out cast polymerization, relative to 100 mass parts of paste resin, CR-570 of 0.12 mass parts as the EDMA and 10.5 mass parts of monomer (B) as phosphorus flame retardant (C) is added, at room temperature It is made it dissolve while stirring 10 minutes.After addition CR-570 after 1 hour, 0.2 mass parts are added as amphipathic chemical combination The SDS of object (E), tertiary own 0.3 mass parts of ester of peroxidating neopentanoic acid as polymerization initiator, dissolved product is set as polymerizeing Property composition (X3), immediately begins to polymerize, obtains resin-formed body using method similarly to Example 1.It will be obtained Resin-formed body evaluation result is shown in table in 5.
[comparative example 2]
The additive amount of phosphorus flame retardant (C) is changed as documented by table 3,5, in addition to this, using with The same method of comparative example 1 obtains resin-formed body.By resin-formed body obtained evaluation result is shown in table in 5.
[comparative example 3,4]
The additive amount of amphiphilic compound (E) is changed as documented by table 3,5, in addition to this, is used Method similarly to Example 1 obtains resin-formed body.By resin-formed body obtained evaluation result is shown in table in 5.
[comparative example 5]
(1) manufacture of paste resin (A2)
In the reactor (polymeric kettle) for having cooling tube, thermometer and blender, investment by MMA91 mass parts, The monomer composition that TBMA8 mass parts, BA1 mass parts are constituted.Above-mentioned monomer composition is maintained at room temperature, on one side with nitrogen drum After bubble is stirred on one side, heated up while stirring until temperature 60 C.Then, relative to above-mentioned monomer composition 100 Mass parts add 2,2 '-azo two (2,4- methyl pentane nitrile) 0.1 mass parts as radical polymerization initiator, will be above-mentioned Monomer composition is heated up while stirring until after 100 DEG C of temperature, is kept for 13 minutes.Then, it carries out cooling until reaction The interior temperature of device become room temperature, obtain by 70 mass % of 30 mass % of polymer and monomer composition (detail be MMA91 matter Measure %, BA1 mass %) constitute paste resin (A2).
(2) cast polymerization
Relative to 100 mass parts of above-mentioned paste resin (A2), EDMA of 0.12 mass parts as monomer (B) is added, in room temperature It is lower to be made it dissolve while stirring 10 minutes, obtain monomer composition (X1).Further at above-mentioned monomer composition (X1) SDS (dioctyl sodium sulphosuccinate) 0.2 mass parts of the middle addition as amphiphilic compound (E), are stirred on one side at room temperature It makes it dissolve on one side within 10 minutes, obtains mixture (X2).Then, CR- of 10.5 mass parts of addition as phosphorus flame retardant (C) 570, dissolved product is set as polymerism combination by tertiary own 0.3 mass parts of ester of peroxidating neopentanoic acid as polymerization initiator Object (X3).
Using the polymerizable composition, polymerizable composition (X3), starts to polymerize using method similarly to Example 1, obtain resin forming Body.By resin-formed body obtained evaluation result is shown in table in 5.
[comparative example 6]
The additive amount of phosphorus flame retardant (C) is changed as documented by table 3,5, in addition to this, using with The same method of comparative example 5 obtains resin-formed body.By resin-formed body obtained evaluation result is shown in table in 5.
It is observed by the resin-formed body that Examples 1 to 3 obtains using optical microscopy, is not as a result observed phosphorus system The dispersed particle of fire retardant (C), anti-flammability (JIS), heat resistance are good.
It is observed by the resin-formed body that embodiment 4~6 obtains using optical microscopy, is not as a result observed phosphorus system The dispersed particle of fire retardant (C), the anti-flammability in anti-flammability (JIS), UL94 testing vertical flammability method are (hreinafter referred to as fire-retardant Property (UL94)), heat resistance it is good.
It is observed by the resin-formed body that embodiment 7 obtains using optical microscopy, as a result observes dispersion particle diameter For the particle of 0.8 μm of phosphorus flame retardant (C), but anti-flammability (JIS) and heat resistance are good.
The resin-formed body obtained by embodiment 8 does not observe the dispersed particle of phosphorus flame retardant (C), anti-flammability (JIS) It is good with heat resistance.
It is observed by the resin-formed body that embodiment 9 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, anti-flammability (JIS), heat resistance are good.
It is observed by the resin-formed body that embodiment 10 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, anti-flammability (JIS and UL94), heat resistance are good.
It is observed by the resin-formed body that embodiment 11 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, anti-flammability (JIS), heat resistance are good.
It is observed by the resin-formed body that embodiment 12 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, anti-flammability (JIS and UL94), heat resistance are good.
It is observed by the resin-formed body that embodiment 13 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, anti-flammability (JIS), heat resistance are good.
It is observed by the resin-formed body that embodiment 14 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, anti-flammability (JIS and UL94), heat resistance are good.
It is observed by the resin-formed body that embodiment 15 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, anti-flammability (JIS), heat resistance are good.
On the other hand, resin-formed body obtained by comparative example 1 observes that dispersion particle diameter is more than 0.8 in resin-formed body μm phosphorus flame retardant (C) particle, D1And D2Value it is bigger than embodiment 1.In addition, the anti-flammability (JIS) of resin-formed body is not filled Point.
The resin-formed body obtained by comparative example 2 observes that dispersion particle diameter is more than 0.8 μm of phosphorus system in resin-formed body The anti-flammability (JIS and UL94) of the particle of fire retardant (C), resin-formed body is insufficient.
The resin-formed body obtained by comparative example 3 observes that dispersion particle diameter is more than 0.8 μm of phosphorus system in resin-formed body The anti-flammability (JIS) of the particle of fire retardant (C), resin-formed body is insufficient.
It is observed by the resin-formed body that comparative example 4 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, but SDS (dioctyl sodium sulphosuccinate) amount is more, therefore anti-flammability (JIS) is insufficient.
It is observed by the resin-formed body that comparative example 5 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, but due to being free of (methyl) acrylate (M), anti-flammability (JIS) is insufficient.
It is observed by the resin-formed body that comparative example 6 obtains using optical microscopy, is not as a result observed that phosphorus system hinders The dispersed particle of agent (C) is fired, but due to being free of (methyl) acrylate (M), anti-flammability (UL94) is insufficient, heat resistance It is low.
[table 2]
[table 3]
* 1 ratio relative to 100 mass parts of monomer composition (X1)
[table 4]
[table 5]
* 2 ratio relative to 100 mass parts of (methyl) propionic acid based polymer (P)
[embodiment 16]
(1) manufacture of paste resin (A3)
In the reactor (polymeric kettle) for having cooling tube, thermometer and blender, MMA70 mass parts, conduct are put into The above-mentioned monomer composition of IBXMA30 part of (methyl) acrylate (M).Above-mentioned monomer composition is maintained at room temperature, on one side After being stirred on one side with nitrogen bubbling, heated up while stirring until temperature 60 C.Then, relative to above-mentioned monomer group 100 mass parts of object are closed, 2,2 '-azo two (2,4- methyl pentane nitrile) 0.1 mass parts as radical polymerization initiator are added, Above-mentioned monomer composition is heated up while stirring until being kept for 13 minutes after 100 DEG C of temperature.Then, it carries out cooling straight Interior temperature to reactor becomes room temperature, obtains by 70 mass % (detail MMA70 of 30 mass % of polymer and monomer composition Quality %, IBXMA30 mass %) constitute paste resin (A3).
(2) cast polymerization
Relative to 100 mass parts of above-mentioned paste resin (A3), the EDMA0.15 mass parts as monomer (B) are added, in room temperature It is lower to be made it dissolve while stirring 10 minutes, obtain monomer composition (X1).Further at above-mentioned monomer composition (X1) SDS (dioctyl sodium sulphosuccinate) 0.2 mass parts of the middle addition as amphiphilic compound (E), are stirred on one side at room temperature It makes it dissolve on one side within 10 minutes, obtains mixture (X2).Then, CR- of 19.0 mass parts of addition as phosphorus flame retardant (C) 570, as tertiary own 0.3 mass parts of ester of the peroxidating neopentanoic acid of polymerization initiator, dissolved product is set as polymerism combination Object (X3).
Peripheral part between 2 SUS plates arranged opposite, so that the gapping interval of 2 SUS plates becomes the side of 4.1mm Vinyl chloride resin washer is arranged in formula, produces casting mold.It modulates above-mentioned polymerizable composition, polymerizable composition (X3) and stands 168 hours later, so Afterwards, polymerizable composition, polymerizable composition (X3) is injected in above-mentioned casting mold, after being fully sealed using vinyl chloride resin washer, immediately Heating is kept for 30 minutes up to 82 DEG C, and then heating is kept for 30 minutes up to 130 DEG C, gathers polymerizable composition, polymerizable composition (X3) It closes.That is, since the time until polymerizeing until adding phosphorus flame retardant (C) be 168 hours.Then, cooling until room temperature Afterwards, it removes SUS plate and obtains the resin-formed body of the plate of thickness 3mm.
2mg is cut from the formed body obtained, finds out the half width at the peak of decomposition product and the generation temperature of decomposition product.Separately Outside, m/z100 is used as methyl methacrylate；Side chain as (methyl) acrylate (M) is detached from object and uses m/ z93；M/z76 is used as phosphorus flame retardant (C).
In addition, cutting out the test film of anti-flammability evaluation using cutting machine from the resin-formed body obtained and heat resistance being commented Then valence test film grinds the face after the cutting out of test film with milling machine.The evaluation result of resin-formed body is shown in In table 7.Resin-formed body obtained has good anti-flammability in terms of anti-flammability (JIS and UL94), and heat resistance is 81 DEG C, well.
[embodiment 17~21]
The type of (methyl) acrylate (M) is set as documented by table 6, it is in addition to this, same with embodiment 16 It operates to sample, obtains resin-formed body.By resin-formed body evaluation result is shown in table in 7.The resin of embodiment 17,18 at Anti-flammability (JIS and UL94), the heat resistance of type body are good.In the resin-formed body of embodiment 19~21, (methyl) acrylate (M) half width of decomposition product is more than 26, and (Ta-Tm) is less than 100, therefore anti-flammability (JIS) is slightly lower.
[embodiment 22]
As documented by table 6, the type of (methyl) acrylate (M) is set as and is used methacrylate (M1) and Acrylate (M2) operates similarly to Example 16 in addition to this, obtains resin-formed body.By commenting for resin-formed body Valence result is shown in Table 7.Anti-flammability (JIS and UL94), the heat resistance of the resin-formed body of embodiment 22 are good.
[embodiment 23,24]
The type of phosphorus flame retardant (C) and additive amount are set as documented by table 6, in addition to this, with embodiment 15 operate in the same way, and obtain resin-formed body.By resin-formed body evaluation result is shown in table in 7.Embodiment 23 and 24 Anti-flammability (JIS), the heat resistance of resin-formed body are good.
[embodiment 25]
The additive amount of (methyl) acrylate (M) is set as documented by table 6, in addition to this, with embodiment 16 It operates in the same way, obtains resin-formed body.By resin-formed body evaluation result is shown in table in 7.The resin of embodiment 25 at Anti-flammability (JIS), the heat resistance of type body are good.
[table 6]
[table 7]
[embodiment 26]
The manufacture of (Production Example 1) multiplet acrylic acid series copolymer particle (rubber A)
1. the modulation of mixture (a-1)
MMA35 parts, BA5 parts, BDMA1 parts, AMA0.15 parts, DBP0.08 parts, (1) 1.4 part of emulsifier are mixed, obtained Obtained mixture (a-1).
2. the modulation of mixture (a-2)
SFS0.2 parts, 5 parts of deionized water are mixed, mixture (a-2) is obtained.
3. the modulation of mixture (a-3)
ST10 parts, BA50 parts, BDMA0.2 parts, AMA1.2 parts, CHP0.2 parts, (1) 2.0 part of emulsifier are carried out mixing to obtain Obtained mixture (a-3).
4. the modulation of mixture (a-4)
SFS0.2 parts, 5 parts of deionized water are subjected to mixing and obtain mixture (a-4).
5. the modulation of mixture (a-5)
MMA57.0 parts, BA3.0 parts, DBP0.1 parts, n-OM0.2 parts are subjected to mixing and obtain mixture (a-5).
6. the manufacture of multiplet acrylic acid series copolymer particle (rubber A)
In the reaction vessel with reflux cooler, 300 parts of ion exchange water, 0.09 part of sodium carbonate, boric acid 0.9 are added Part, it being warming up to while stirring after 80 DEG C, 2.6 parts in 42.63 parts of addition said mixture (a-1) are kept for 15 minutes, Then remaining said mixture (a-1) is continuously added with the speed of 5.5 parts/hour, is then kept for 1 hour, carried out most The polymerization of internal layer.
Then, 5.2 parts of said mixture (a-2) is added, after being kept for 15 minutes, by 63.6 parts of said mixture (a-3) It is continuously added with the speed of 5.1 parts/hour, is then kept for 2.5 hours, carry out the polymerization of middle layer.
Then, 5.2 parts of said mixture (a-4) is added, after being kept for 15 minutes, by 60.3 parts of said mixture (a-5) It is continuously added with the speed of 0.6 part/hour, is then kept for 1 hour, carry out outermost polymerization, obtain multiplet third Olefin(e) acid based copolymer latex.
Then, which is solidified with calcium acetate aqueous solution, is washed, be dehydrated, dried, obtains multiplet The particle (rubber A) of acrylic acid series copolymer.
(1) manufacture of paste resin (A4)
In the reactor (polymeric kettle) for having cooling tube, thermometer and blender, investment by MMA71 mass parts, The monomer composition that IBXMA25 mass parts, IBXA1 mass parts, TBMA2 mass parts, BA1 mass parts are constituted.By above-mentioned monomer group It closes object and is maintained at room temperature, after being stirred while being bubbled with nitrogen, heated up while stirring until temperature 60 C.It connects , relative to above-mentioned 100 mass parts of monomer composition, add 2, the 2 '-azos two (2,4- bis- as radical polymerization initiator Methyl valeronitrile) 0.02 mass parts, above-mentioned monomer composition are heated up while stirring until keeping 13 after 100 DEG C of temperature Minute.Then, carry out cooling until the interior temperature of reactor is obtained as room temperature by 5 mass % of polymer and monomer composition The paste resin (A4) that 95 mass % are constituted.
(2) cast polymerization
Relative to above-mentioned paste resin (A4), the EDMA0.15 mass parts as monomer (B) are added, are stirred on one side at room temperature It makes it dissolve on one side within 10 minutes, obtains monomer composition (X1).Conduct is further added in above-mentioned monomer composition (X1) 0.2 mass parts of SDS (dioctyl sodium sulphosuccinate) of amphiphilic compound (E) and the rubber as impact resistance modifier (D) A7.5 mass parts make it dissolve while stirring 10 minutes at room temperature, obtain mixture (X2).Then, 13.6 are added Tertiary own 0.3 mass parts of ester of CR-570 of the mass parts as phosphorus flame retardant (C), the peroxidating neopentanoic acid as polymerization initiator, Dissolved product is set as polymerizable composition, polymerizable composition (X3).
Peripheral part between 2 SUS plates arranged opposite, so that the gapping interval of 2 SUS plates becomes the side of 4.1mm Resin washer is arranged in formula, produces casting mold.It modulates above-mentioned polymerizable composition, polymerizable composition (X3) and stands 168 hours later, then upper It states in casting mold, injects polymerizable composition, polymerizable composition (X3), after being fully sealed with resin washer, heating immediately is kept up to 82 DEG C 30 minutes, then heating was kept for 30 minutes up to 130 DEG C, polymerize polymerizable composition, polymerizable composition (X3).That is, from the resistance of addition phosphorus system Time of combustion agent (C) until starting polymerization is 168 hours.Then, cooling after room temperature, it removes SUS plate and obtains The resin-formed body of the plate of thickness 3mm.
Using cutting machine, test film, the charpy impact intensity of anti-flammability evaluation are cut out from resin-formed body obtained The test film of evaluation and the test film of weatherability evaluation.In addition, for the test film and charpy impact of anti-flammability evaluation The test film of intensity evaluation cuts end face with milling machine.By resin-formed body obtained evaluation result is shown in table 9 In.The anti-flammability (JIS) of resin-formed body well, and charpy impact intensity be 35kJ/m2, weatherability (Δ YI) is 5, well.
[embodiment 27]
The additive amount of impact resistance modifier (D) is set as documented by table 8, it is in addition to this, same with embodiment 26 It operates to sample, obtains resin-formed body.By resin-formed body evaluation result is shown in table in 9.The resin forming of embodiment 27 Anti-flammability (JIS), weatherability, the charpy impact intensity of body are good.
[embodiment 28]
The manufacture of (Production Example 2) multiplet acrylic acid series copolymer particle (rubber B)
1. the modulation of mixture (b-1)
By MMA23 parts, ST1 parts, BA16 parts, BDMA1 parts, AMA0.15 parts, DBP0.08 parts, (1) 1.4 part of emulsifier progress Mixing, obtains mixture (b-1).
2. the modulation of mixture (b-2)
SFS0.2 parts, 5 parts of deionized water are mixed, mixture (b-2) is obtained.
3. the modulation of mixture (b-3)
ST10 parts, BA50 parts, BDMA0.2 parts, AMA1.2 parts, CHP0.2 parts, (1) 2.0 part of emulsifier are mixed, obtained Obtained mixture (b-3).
4. the modulation of mixture (b-4)
SFS0.2 parts, 5 parts of deionized water are mixed, mixture (b-4) is obtained.
5. the modulation of mixture (b-5)
MMA57.0 parts, MA3.0 parts, DBP0.1 parts, n-OM0.2 parts are mixed, mixture (b-5) is obtained.
6. the manufacture of multiplet acrylic acid series copolymer particle (rubber B)
In the reaction vessel with reflux cooler, 300 parts of ion exchange water, 0.09 part of sodium carbonate, boric acid 0.9 are added Part, it is warming up to after 80 DEG C, 2.5 parts in 41.33 parts of addition said mixture (b-1) are kept for 15 minutes, then will be remaining Said mixture (b-1) is continuously added with 5.4 mass parts/hour speed, is then kept for 1 hour, is carried out the polymerization of innermost layer.
Then, 5.2 parts of said mixture (b-2) is added, after being kept for 15 minutes, by 63.6 parts of said mixture (b-3) It is continuously added with the speed of 5.1 parts/hour, is then kept for 2.5 hours, carry out the polymerization of middle layer.
Then, 5.2 parts of said mixture (b-4) is added, after being kept for 15 minutes, by 61.3 parts of said mixture (b-5) It is continuously added with the speed of 0.61 part/hour, is then kept for 1 hour, carry out outermost polymerization, obtain multiplet third Olefin(e) acid based copolymer latex.
Then, which is solidified with calcium acetate aqueous solution, is washed, be dehydrated, dried, obtains multiplet The particle (rubber B) of acrylic acid series copolymer.
7.5 parts of rubber B as impact resistance modifier (D) are added, in addition to this, operates, obtains similarly to Example 26 Obtained resin-formed body.By resin-formed body evaluation result is shown in table in 9.The anti-flammability of the resin-formed body of embodiment 28 (JIS), weatherability, charpy impact intensity are good.
[embodiment 29]
Add the commercially available acrylic block copolymer (trade name as impact resistance modifier (D)：KURARITY, Kuraray Co. Ltd. system) 7.5 parts, in addition to this, operation obtains resin-formed body similarly to Example 26.By resin Formed body evaluation result is shown in table in 9.The anti-flammability (JIS) of the resin-formed body of embodiment 29, weatherability, charpy impact are strong Degree is good.
[table 8]
[table 9]
[embodiment 30]
(1) solidify the manufacture of envelope (F)
It is being 40 mass %, as the two of polyfunctional monomer (F2) by the polyacrylate 1 as polyfunctional monomer (F1) Acrylate 1 is that above-mentioned solidification compound (f) is set as 100 mass in the solidification compound (f) that 60 mass % are constituted Part, add BEE of 1.5 mass parts as Photoepolymerizationinitiater initiater, and mixed (hereinafter, be added to Photoepolymerizationinitiater initiater it Solidification compound afterwards is also referred to as " solidification compound (f) ".).
Then, on the SUS304 plate of mirror-like, above-mentioned solidification compound (f), the PET that 12 μm of cladding thickness are coated with Film, it is on a pet film, spreadable using 40 ° of rubber rollers of JIS hardness, it is formed on SUS304 plate by above-mentioned solidification compound (f) The layer of formation.
Then, make the SUS304 plate for being formed with the layer of solidification compound (f), passed through on one side with 2m/ minutes speed glimmering Light ultraviolet radiator (Toshiba's (strain) system, trade name：FL40BL, output power 40W's) lower section 20cm position, on one side across PET film carries out curing process, then removes PET film to the light of above-mentioned solidification compound (f) irradiation fluorescent ultra-violet lamp.
Then, make the SUS304 plate for being formed with the layer of the above-mentioned solidification compound (f) after curing process, on one side with 3m/ The speed of minute passes through high-pressure mercury-vapor lamp (output power 30W/cm2) lower section 20cm position, on one side to above-mentioned curability group The ultraviolet light of object (f) irradiation high-pressure mercury-vapor lamp is closed, further progress curing process forms 20 μm of film thickness on SUS304 plate Solidify envelope (F).Same operation is repeated, obtains and is formed with 2 SUS304 plates for solidifying envelope (F).
(2) production of casting mold
Make to be formed with 2 SUS304 plates for solidifying envelope (F) by be formed with solidify envelope (F) face be in inside in a manner of Resin washer is arranged in a manner of making gapping interval become 4.1mm, by it in opposed, between 2 SUS304 plates peripheral part It is set as casting mold.
(3) manufacture of paste resin (A5)
In the reactor (polymeric kettle) for having cooling tube, thermometer and blender, supply MMA67 mass parts, The mixture of IBXMA25 mass parts, IBXA5 mass parts, TBMA2 mass parts and BA1 mass parts, is stirred on one side, uses nitrogen on one side After being bubbled, begin to warm up.At the time of temperature becomes 60 DEG C inside, 2,2 '-idols of the addition as radical polymerization initiator 0.1 part of nitrogen two (2,4- methyl pentane nitrile), further heating is kept for 13 minutes until after 100 DEG C of interior temperature.Then, it will react Device is cooling until room temperature, and to obtain is 30 mass % by polymer, monomer composition is paste resin (A5) that 70 mass % are constituted.
(4) cast polymerization
In 100 mass parts of above-mentioned paste resin (A5), the EDMA0.15 mass parts as monomer (B) are added, at room temperature It is made it dissolve while stirring 10 minutes, obtains monomer composition (X1).Further in above-mentioned monomer composition (X1) 0.2 mass parts of SDS (dioctyl sodium sulphosuccinate) as amphiphilic compound (E) are added, stir 10 on one side at room temperature Minute makes it dissolve on one side, obtains mixture (X2).Then, CR- of 13.6 mass parts of addition as phosphorus flame retardant (C) 570, as tertiary own 0.3 mass parts of ester of the peroxidating neopentanoic acid of polymerization initiator, dissolved product is set as polymerism combination Object (X3).
Then, after modulating above-mentioned polymerizable composition, polymerizable composition (X3), 168 hours are stood, then in above-mentioned casting mold, injection is poly- Conjunction property composition (X3) after being fully sealed with resin washer, heats 30 minutes at 82 DEG C, then heats 30 points at 130 DEG C Clock, it is cooling until room temperature after polymerizeing polymerizable composition, polymerizable composition (X3).Then, SUS plate is removed, the plate of thickness 3mm is obtained Laminated resin body.
Using cutting machine, the test film of anti-flammability evaluation is cut out from laminated resin body obtained and Evaluation of Heat Tolerance is used Then test film grinds the face after the cutting out of test film with milling machine.By laminated resin body evaluation result is shown in table 11 In.Laminated resin body obtained has anti-flammability in terms of the evaluation of anti-flammability (JIS), and heat resistance is 95 DEG C, weather-proof Property (Δ YI) be 3, furthermore pencil hardness be 4H, well.
[embodiment 31]
The additive amount of phosphorus flame retardant (C) is changed as documented by table 10, in addition to this, using with reality The same method of example 30 is applied, laminated resin body is obtained.By laminated resin body obtained evaluation result is shown in table in 11.Institute The laminated resin body of acquisition has good anti-flammability in terms of the evaluation of anti-flammability (JIS, UL94), and heat resistance is 82 DEG C, weatherability (Δ YI) is 3, and furthermore pencil hardness is 4H, well.
[embodiment 32,33]
The additive amount of the composition for solidifying the solidification compound (f) of envelope (F) and phosphorus flame retardant (C) is set as such as table 10 It is shown such, it in addition to this, operates similarly to Example 30, obtains laminated resin body.By laminated resin body obtained Evaluation result is shown in table in 11.The laminated resin body obtained by embodiment 32 has resistance in terms of the evaluation of anti-flammability (JIS) Combustion property, and heat resistance is 95 DEG C, and weatherability (Δ YI) is 3, and furthermore pencil hardness is 8H, well.In addition, being obtained by embodiment 33 The laminated resin body obtained has good anti-flammability in terms of the evaluation of anti-flammability (JIS, UL94), and heat resistance is 82 DEG C, Weatherability (Δ YI) is 3, and furthermore pencil hardness is 8H, well.
[table 10]
[table 11]
Industry utilizability
By means of the invention it is possible to which steadily providing has good heat resistance, further with (methyl) of high flame retardant Acrylic resin composition, and the resin-formed body formed by above-mentioned (methyl) acrylic resin composition.It is such Resin-formed body can require the purposes of high flame retardant suitable for billboard etc..
Symbol description
1 solidification envelope
2 resin base materials
3 laminated resin bodies.

Claims (32)

1. a kind of (methyl) acrylic resin composition, is containing (methyl) acrylic acid series polymeric compounds (P), phosphorus flame retardant (C) and (methyl) acrylic resin composition of amphiphilic compound (E),
(methyl) the acrylic resin composition contains relative to 100 mass parts of (methyl) acrylic acid series polymeric compounds (P) There are 5.0 mass parts of the phosphorus flame retardant (C) or more 35.0 below the mass, also,
(methyl) the acrylic resin composition contains relative to 100 mass parts of (methyl) acrylic acid series polymeric compounds (P) There are 0.01 mass parts of the amphiphilic compound (E) or more 2.0 below the mass, also, has JIS K 6911-1995's In fire resistance test A method within 3 minutes self-extinguishment anti-flammability.
2. (methyl) acrylic resin composition according to claim 1, (methyl) acrylic acid series polymeric compounds (P) To include (methyl) acrylate (M) from side chain with the alicyclic type hydrocarbon of aromatic hydrocarbyl or carbon atom number 3~20 Repetitive unit polymer.
3. a kind of (methyl) acrylic resin composition, is containing (methyl) acrylic acid series polymeric compounds (P), phosphorus flame retardant (C) and (methyl) acrylic resin composition of amphipathic chemical combination (E),
(methyl) acrylic acid series polymeric compounds (P) are comprising having aromatic hydrocarbyl or carbon atom number 3~20 from side chain Alicyclic type hydrocarbon (methyl) acrylate (M) repetitive unit polymer,
The dispersion particle diameter of the phosphorus flame retardant (C) in (methyl) the acrylic resin composition is 0.8 μm hereinafter, simultaneously And there is the anti-flammability of the self-extinguishment within 3 minutes in the fire resistance test A method of JIS K 6911-1995.
4. (methyl) acrylic resin composition according to claim 3, (methyl) acrylic resin composition phase For 100 mass parts of (methyl) acrylic acid series polymeric compounds (P), more than 5.0 mass parts of the phosphorus flame retardant (C) 35.0 below the mass with more than 0.01 mass parts of amphiphilic compound (E) 2.0 below the mass.
5. (methyl) acrylic resin composition according to any one of claims 1 to 4, the amphiphilic compound It (E) is anionic surfactant.
6. (methyl) acrylic resin composition according to claim 5, the anionic surfactant is alkane The alkali metal salt of base sulfosuccinic acid.
7. (methyl) acrylic resin composition according to claim 6, the alkali metal of the alkyl sulfosuccinic Salt is dioctyl sodium sulphosuccinate.
8. (methyl) acrylic resin composition according to any one of claims 1 to 5, the phosphorus flame retardant (C) for selected from least one of phosphate containing halogen and phosphonate ester containing halogen, the amphiphilic compound (E) is following chemistry Non-halogen phosphoric ester shown in formula (I),
In formula (I), R indicate alkyl, naphthenic base, aryl, alkoxy, alkoxy carbonyl, alkyl carboxyl, alkylidene, cycloalkylidene, Arlydene, aryl alkylene, polyoxyalkylenes, n are 1 or 2.
9. (methyl) acrylic resin composition according to claim 8, in the formula (I), R be carbon atom number 2~ 24 aliphatic alkyl.
10. (methyl) acrylic resin composition described according to claim 1~any one of 9, (methyl) propylene Sour based polymer (P) is the gross mass relative to (methyl) acrylic acid series polymeric compounds (P), comprising deriving from methyl methacrylate 19.95 mass % of repetitive unit or more, 84.95 mass % hereinafter, and from described (methyl) acrylate (M) repetition 3.6 mass % of unit or more, 80.0 mass % polymer below.
11. (methyl) acrylic resin composition according to claim 10,
(methyl) acrylic acid series polymeric compounds (P) include to have aromatic hydrocarbyl or carbon atom number 3~20 from side chain The repetitive unit of the methacrylate (M1) of alicyclic type hydrocarbon and from side chain have aromatic hydrocarbyl or carbon atom number 3~ The repetitive unit of the acrylate (M2) of 20 alicyclic type hydrocarbon is as the repetition list from described (methyl) acrylate (M) Member, also,
Comprising from the methacrylate (M1) 10.0 mass % of repetitive unit or more, 79.5 mass % hereinafter,
From 0.50 mass % of repetitive unit or more, the 20.0 mass % or less of the acrylate (M2).
12. (methyl) acrylic resin composition described in 0 or 11 according to claim 1, (methyl) acrylic acid series is poly- Closing object (P) is the gross mass relative to (methyl) acrylic acid series polymeric compounds (P), comprising having 2 or more alkene in molecule Belong to 0.05 mass % of structural unit or more, the 0.40 mass % polymer below of the monomer (B) of unsaturated bond.
13. (methyl) the acrylic resin composition according to any one of claim 2~12, utilizes following measurement sides The half width that method 1 measures the peak of the decomposition product of repetitive unit obtaining, from described (methyl) acrylate (M) is 26 DEG C hereinafter,
Measuring method 1：
Using gas analysis measurement device (EGA-MS) occurs, it is in flow velocity by (methyl) acrylic resin composition 2mg Under 20ml/ minutes helium atmospheres, with 10 DEG C/min of heating rate, the mass spectral analysis of the generation gas of decomposition product is carried out, is asked The half width at the peak of the decomposition product in temperature-chromatographic curve obtained out.
14. (methyl) the acrylic resin composition according to any one of claim 2~13, by following measuring methods The generation temperature and phosphorus system resistance of the decomposition product of 2 repetitive units from described (methyl) acrylate (M) obtained The generation temperature for firing the decomposition product of agent (C) meets following formula (1),
|Tm-Tc|≤40 ···(1)
Tc：The generation temperature of phosphorus flame retardant (C) decomposition product, unit be DEG C,
Tm：From the generation temperature of the decomposition product of the repetitive unit of (methyl) acrylate (M), unit is DEG C,
Measuring method 2：
Using gas analysis measurement device (EGA-MS) occurs, it is in flow velocity by (methyl) acrylic resin composition 2mg Under 20ml/ minutes helium atmospheres, with 10 DEG C/min of heating rate, the mass spectral analysis of the generation gas of decomposition product is carried out, is found out The generation temperature of decomposition product in temperature-chromatographic curve of acquisition.
15. (methyl) acrylic resin composition according to claim 14, the source obtained by the measuring method 2 In the generation temperature of the decomposition product of the repetitive unit of (methyl) acrylate (M) and from the methyl methacrylate The generation temperature of the decomposition product of the repetitive unit of ester meets following formula (2),
100≤Ta-Tm ···(2)
Ta：From the generation temperature of the decomposition product of the repetitive unit of methyl methacrylate, unit is DEG C.
16. (methyl) acrylic resin composition described in any one of 3~15, the half width are according to claim 1 21 DEG C or less.
17. (methyl) acrylic resin composition described according to claim 1~any one of 16,
For use the relaxation spectrum observed using solid NMR measurement device by spin lock cross polarization method MC (τ) and MP (τ), the value D being calculated by following formula (a)1(%), the value D in spin lock time τ=30msec1(%) is 6.0 (%) Hereinafter,
D1(%)=| MC (τ)-MP (τ) |/MC (τ) × 100 (a)
MC(τ)：The average value of the value of following (A) and (B)
When (A) by spin lock time τ sec13160ppm~180ppm of C nuclear ralaxation spectrum is observed right with the carbon institute of carbonyl When the area for the spectrum answered is divided by 10 μ sec of spin lock time13C nuclear ralaxation spectrum 160ppm~180ppm observed with The value that the area of spectrum corresponding to the carbon of carbonyl obtains,
When (B) by spin lock time τ sec1330ppm~65ppm of C nuclear ralaxation spectrum is observed right with the carbon institute of methylene When the area for the spectrum answered is divided by 10 μ sec of spin lock time13C nuclear ralaxation spectrum 30ppm~65ppm observed with Asia The value that the area of spectrum corresponding to the carbon of methyl obtains,
MP(τ)：When by spin lock time τ sec31P nuclear ralaxation spectrum -40~40ppm observed with phosphorus flame retardant (C) Phosphorus atoms corresponding to spectrum area divided by 10 μ sec of spin lock time when31- 40~40ppm of P core spectrum is observed To the phosphorus atoms with phosphorus flame retardant (C) corresponding to spectrum the obtained value of area.
18. (methyl) acrylic resin composition according to claim 17, (methyl) the acrylic resin group It closes in object, for the value D being calculated by the formula (a)1(%), spin lock time τ=16msec, 20msec, 25msec, Each value D when 30msec1The average value D of (%)2(%) is 7.0% or less.
19. (methyl) acrylic resin composition described in 7 or 18 according to claim 1, the phosphate and phosphonate ester Weight average molecular weight is 200 or more 500 or less.
20. (methyl) acrylic resin composition described according to claim 1~any one of 19, (methyl) propylene Sour based resin composition includes multiplet acrylic acid series copolymer particle (D1) or acrylic block selected from following records At least one of copolymer (D2) impact resistance modifier (D),
Multiplet acrylic acid series copolymer particle (D1)：With in the elasticity comprising the rubbery copolymer with cross-linked structure The multiplet acrylic acid series copolymer particle of the structure of hard resin layer (d1-2) is formed on the surface of body particle (d1-1),
Acrylic block copolymer (D2)：With 10 mass % of methacrylate block (d2-1) or more, 60 mass % Below with 40 mass % of acrylic ester polymerization block (d2-2) or more, 90 mass % block copolymer below.
21. (methyl) acrylic resin composition according to claim 20, (methyl) the acrylic resin group Object is closed relative to 100 mass parts of (methyl) acrylic acid series polymeric compounds (P), includes 2.0 mass of impact resistance modifier (D) Part or more 50 below the mass.
22. (methyl) acrylic resin composition according to claim 21, the multiplet acrylic copolymer In object particle (D1), constitute the elastomer particle (d1-1) rubbery copolymer include using alkyl acrylate as it is main at The (co) polymer divided, the hard resin layer (d1-2) include using methacrylate as the (co) polymer of principal component.
23. a kind of resin-formed body, it includes (methyl) the acrylic resin combinations described in any one of claim 1~22 Object.
24. a kind of laminated resin body is that at least one surface of the resin-formed body described in claim 23 has solidification The laminated resin body of the sheet of envelope (F),
The envelope (F) that solidifies is formed by the solidfied material of solidification compound (f), and the solidification compound (f), which is contained, has 3 The polyfunctional monomer (F1) of a above (methyl) acryloyl group and the polyfunctional monomer (F2) with 2 (methyl) acryloyl groups.
25. laminated resin body according to claim 24, the solidification compound (f) contains the polyfunctional monomer (F1) 50 mass % or more, 80 mass % or less the and polyfunctional monomer (F2) 20 mass % or more, 50 mass % or less.
26. the manufacturing method of (methyl) acrylic resin composition described in any one of claim 2~19, it includes under Process 1 and process 2 are stated,
Process 1：In the mixture (X2) containing monomer composition (X1) and amphiphilic compound (E), phosphorus flame retardant is added (C) come the process for obtaining polymerizable composition, polymerizable composition (X3), the monomer composition (X1) includes that side chain has aromatic hydrocarbyl or carbon (methyl) acrylate (M) monomer of the alicyclic type hydrocarbon of atomicity 3~20,
Process 2：The process that the polymerizable composition, polymerizable composition (X3) is polymerize.
27. the manufacturing method of (methyl) acrylic resin composition, is claim 20~22 described in claim 20 Any one of described in (methyl) acrylic resin composition manufacturing method, in the process 1, the mixture (X2) Containing amphiphilic compound (E) and impact resistance modifier (D), the impact resistance modifier (D) is selected from multiplet acrylic acid At least one of based copolymer particle (D1) or acrylic block copolymer (D2),
Multiplet acrylic acid series copolymer particle (D1)：With in the elasticity comprising the rubbery copolymer with cross-linked structure The multiplet acrylic acid series copolymer particle of the structure of hard resin layer (d1-2) is formed on the surface of body particle (d1-1),
Acrylic block copolymer (D2)：With 10 mass % of methacrylate block (d2-1) or more, 60 mass % Below with 40 mass % of acrylic ester polymerization block (d2-2) or more, 90 mass % block copolymer below.
28. the manufacturing method of (methyl) acrylic resin composition according to claim 26 or 27, the monomer group The gross mass of object (X1) relative to monomer composition (X1) is closed, includes 19.95 mass % of methyl methacrylate monomer or more 84.95 mass % or less and 3.6 mass % of (methyl) acrylate (M) or more, the 80.0 mass % or less.
29. the manufacturing method of (methyl) acrylic resin composition according to claim 28,
The monomer composition (X1) includes the methyl that side chain has the alicyclic type hydrocarbon of aromatic hydrocarbyl or carbon atom number 3~20 Acrylate (M1) and side chain have acrylate (M2) conduct of the alicyclic type hydrocarbon of aromatic hydrocarbyl or carbon atom number 3~20 (methyl) acrylate (M), also,
The methacrylate (M1) be 10.0 mass % or more, 79.5 mass % hereinafter,
The acrylate (M2) is 0.50 mass % or more, 20.0 mass % or less.
30. the manufacturing method of (methyl) acrylic resin composition according to claim 28 or 29, the monomer group Close object (X1) include molecule in 2 or more ethylenic unsaturated bonds 0.05 mass % of monomer (B) or more, 0.40 mass % with Under.
31. the manufacturing method of (methyl) acrylic resin composition according to any one of claim 26~30,
The monomer composition (X1) is in advance comprising the polymerization containing the repetitive unit from described (methyl) acrylate (M) Object (P1).
32. the manufacturing method of (methyl) acrylic resin composition according to any one of claim 26~31, will The monomer composition (X1) is set as 100 mass parts, and the polymerizable composition, polymerizable composition (X3) contains the phosphorus flame retardant (C) 5.0 It is more than mass parts 35.0 below the mass with more than 0.01 mass parts of the amphiphilic compound (E) 2.0 below the mass.
CN201780018937.3A 2016-03-24 2017-03-17 The manufacturing method of (methyl) acrylic resin composition, resin-formed body, laminated resin body and (methyl) acrylic resin composition Withdrawn CN108884289A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113710454A (en) * 2019-04-23 2021-11-26 住友化学株式会社 Laminate and method for producing laminate

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022196516A1 (en) * 2021-03-18 2022-09-22 三井化学株式会社 Curable composition and optical material obtained therefrom
FR3131327A1 (en) 2021-12-23 2023-06-30 Arkema France (METH)ACRYLIC COMPOSITION, COMPOSITE MATERIAL OBTAINED FROM SUCH A COMPOSITION, METHOD FOR THE PRODUCTION OF SAID COMPOSITION AND CORRESPONDING USES

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014069462A1 (en) * 2012-10-29 2014-05-08 リンテック株式会社 Adhesive sheet
CN104011176A (en) * 2011-10-31 2014-08-27 路博润高级材料公司 Non-halogen flame retardant polymers
JP2015074740A (en) * 2013-10-10 2015-04-20 三菱レイヨン株式会社 Methacrylic resin composition and production method thereof, and resin molding

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11152341A (en) * 1997-11-21 1999-06-08 Mitsubishi Rayon Co Ltd Flame-retardant methacrylic resin plate, its production, and sound-isolating panel
JP2000015631A (en) * 1998-07-03 2000-01-18 Kanegafuchi Chem Ind Co Ltd Thermoplastic resin pellet excellent in moldability
EP1876206A4 (en) * 2005-04-28 2010-07-21 Techno Polymer Co Ltd Thermoplastic resin composition and molding thereof
JP5572286B2 (en) * 2007-12-27 2014-08-13 ユーエムジー・エービーエス株式会社 Reinforced thermoplastic resin composition and molded article
JP2010037486A (en) * 2008-08-07 2010-02-18 Mitsubishi Rayon Co Ltd Acrylic resin composition, and molded product
JP2011046835A (en) * 2009-08-27 2011-03-10 Sumitomo Chemical Co Ltd Methacrylic resin composition
KR20120120387A (en) * 2010-02-02 2012-11-01 가오 가부시키가이샤 Process for production of polylactic acid resin composition
JP2015086250A (en) * 2013-10-28 2015-05-07 株式会社クラレ Methacrylic resin composition and molded body
TWI585144B (en) * 2014-10-21 2017-06-01 Mitsubishi Rayon Co (Meth) acrylic resin composition and a resin molded product

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104011176A (en) * 2011-10-31 2014-08-27 路博润高级材料公司 Non-halogen flame retardant polymers
WO2014069462A1 (en) * 2012-10-29 2014-05-08 リンテック株式会社 Adhesive sheet
JP2015074740A (en) * 2013-10-10 2015-04-20 三菱レイヨン株式会社 Methacrylic resin composition and production method thereof, and resin molding

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113710454A (en) * 2019-04-23 2021-11-26 住友化学株式会社 Laminate and method for producing laminate
CN113710454B (en) * 2019-04-23 2023-06-23 住友化学株式会社 Laminate and method for producing laminate

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