CN1922228A - Graft copolymer, flame retardant composed of such copolymer and resin composition containing such flame retardant - Google Patents
Graft copolymer, flame retardant composed of such copolymer and resin composition containing such flame retardant Download PDFInfo
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- CN1922228A CN1922228A CN 200580005663 CN200580005663A CN1922228A CN 1922228 A CN1922228 A CN 1922228A CN 200580005663 CN200580005663 CN 200580005663 CN 200580005663 A CN200580005663 A CN 200580005663A CN 1922228 A CN1922228 A CN 1922228A
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Abstract
Disclosed is a copolymer with excellent flame retardance/impact resistance improving effects wherein the residual amount of volatile siloxane is reduced. Also disclosed are a flame retardant composed of such a copolymer and a resin composition containing such a flame retardant. Specifically disclosed is a polyorganosiloxane-containing copolymer which is obtained by polymerizing 0-10 parts by weight of a vinyl monomer (D), which is composed of 100-50 weight% of a multifunctional monomer (B) having two or more polymerizable unsaturated bonds and 0-50 weight% of another copolymerizable monomer (C), in the presence of 30-95 parts by weight of a polyorganosiloxane (A) in a latex form which is obtained by emulsion-polymerizing a straight or branched chain siloxane having an end group selected from a hydroxyl group, amino group and hydrolyzable group, and further polymerizing 5-70 parts by weight of a vinyl monomer (E) (with (A), (D) and (E) being 100 parts by weight in total).
Description
Technical field
The present invention relates to the graft copolymer containing polysiloxane, the fire retardant being made of the copolymer and the excellent resin combinations of the anti-flammability and impact resistance that are compounded in thermoplastic resin the fire retardant.
Background technique
Polycarbonate resin is widely used as electrical, electronic component, office equipment, household supplies or construction material due to excellent impact resistance, heat resistance, electrical characteristic etc..Although polycarbonate resin has anti-flammability more higher than polystyrene resins etc., the improvement of anti-flammability is realized by adding various fire retardants in the field that electrical, electronic component, office equipment etc. require high flame retardant.As the non-phosphorus type flame retardant of non-halogen, the utilization of poly organo siloxane compound (also referred to as polysiloxanes) is proposed.So far, as the method for obtaining fire retardant resin composition using poly organo siloxane compound, it is known that method that flame retardant resin is made and being kneaded the polyorganosiloxane resin being made of single organopolysiloxane in non-silicone polymer etc. (referring for example to patent document 1).However, although polyorganosiloxane resin has assigns the effect of anti-flammability but insufficient, and supplementary result is wanted to reduce the impact resistance of resin combination when increasing dosage, there is the project for seldom arriving anti-flammability and impact resistance both excellent fire retardant resin composition.
As the method that the fire retardant resin composition with impact resistance is made using poly organo siloxane compound, it is known that vinyl monomer and the particle grafted graft copolymer and polytetrafluoroethylene (PTFE) containing polysiloxane polymerizeing of polysiloxane less than or equal to 0.2 μm are made by using respective specific quantity, it is compounded into thermoplastic resin that (referring for example to patent documents 2) such as fire retardant resin compositions is made.
On the other hand, it is known by will have selected from hydroxyl, amino, hydrolization group end group straight-chain or branched siloxanes carry out emulsion polymerization, the few latex comprising polysiloxane particle of volatile siloxane is made (referring for example to patent document 3).However the graft copolymer containing polysiloxane made from this latex is used, compared with the graft copolymer containing polysiloxane made from the preparation method as patent document 2, there is the tendency that the anti-flammability obtained with final molding body is low, aesthetic appearance also deteriorates.
Actual state is only to be had both to reduce volatile siloxane and anti-flammability with current art difficulty.
Patent document 1: tekiaki 54-36365 bulletin
Patent document 2: special open 2002-348453 bulletin
Patent document 3: special open 2001-288269 bulletin
Summary of the invention
The purpose of the present invention is to provide the residual quantities of volatile siloxane the reason of reduction when reducing manufacture as significant loss or production efficiency, and fire retardant anti-flammability, impact resistance improvement the excellent graft copolymer containing polysiloxane and be made of the graft copolymer, and it is compounded with the excellent resin combination of anti-flammability, aesthetic appearance, impact resistance of the fire retardant.
The result that the present inventors concentrate on studies repeatedly to the above subject, it was found that by vinyl monomer-grafted be aggregated to as will have selected from hydroxyl, amino, hydrolization group end group straight-chain or branched silicone emulsion polymerization made from latex state polysiloxane on the graft copolymer containing polysiloxane, reduce volatile siloxane, and being somebody's turn to do the graft copolymer containing polysiloxane can be used as fire retardant use, excellent anti-flammability, impact resistance is presented in the thermoplastic resin composition for being compounded with the fire retardant, so as to complete the present invention.
I.e., the present invention relates to the graft copolymers containing polysiloxane, it will be by that will have selected from hydroxyl, amino, in the presence of 30~95 parts by weight of polysiloxane (A) of latex state prepared by the straight-chain or branched silicone emulsion polymerization of the end group of hydrolization group, it will be by containing 100~50 weight % of multi-functional monomer (B) more than or equal to 2 polyunsaturated bonds, 0~10 weight parts of polymer of vinyl monomer (D) that 0~50 weight % of copolymerizable monomer (C) is formed with other, in turn by 5~70 parts by weight ((A) of vinyl monomer (E), (D), (E) add up to 100 parts by weight) it polymerize and is made.
As preferred embodiment, it is related to the graft copolymer containing polysiloxane that vinyl monomer (D) is 0.1~10 parts by weight.
As preferred embodiment, it is related to the graft copolymer containing polysiloxane, it is characterized by: the use of the dissolubility to water being the radical initiator (F) more than or equal to 0.5g/100g (20 DEG C) when (D) and/or (E) polymerize.
As preferred embodiment, it is related to the graft copolymer containing polysiloxane, wherein, vinyl monomer (E) is at least one kind of monomer for being selected from aromatic vinyl base class monomer, vinyl cyanide class monomer, (methyl) acrylic ester monomer and the vinyl monomer containing carboxyl.
In addition, the present invention relates to the fire retardants being made of the graft copolymer containing polysiloxane.
Moreover, it relates to be compounded with resin combination made of above-mentioned 0.1~20 parts by weight of fire retardant relative to 100 parts by weight of thermoplastic resin.
The residual quantity that can be made according to the present invention reduces the volatile siloxane of reason as significant loss or production efficiency when making manufacture is reduced, and the fire retardant of the excellent thermoplastic resin composition of anti-flammability, aesthetic appearance, impact resistance improvement is assigned, and the excellent fire retardant resin composition of anti-flammability, aesthetic appearance, impact resistance can be obtained by being compounded the fire retardant in thermoplastic resin.
Specific embodiment
Graft copolymer containing polysiloxane of the invention, it is by that will have selected from hydroxyl, amino, in the presence of 30~95 parts by weight of latex shape polysiloxane (A) prepared by the straight-chain or branched silicone emulsion polymerization of the end group of hydrolization group, it will be by containing 100~50 weight % of multi-functional monomer (B) more than or equal to 2 polyunsaturated bonds, 0~10 weight parts of polymer of vinyl monomer (D) that 0~50 weight % of copolymerizable monomer (C) is formed with other, in turn by 5~70 parts by weight ((A) of vinyl monomer (E), (D), (E) add up to 100 parts by weight) polymerization prepared by the graft copolymer containing polysiloxane, as fire retardant, it is compounded available display excellent flame retardancy, the thermoplastic resin of impact resistance Oil/fat composition.
Polysiloxane used in the present invention can be made as disclosed in Japanese Unexamined Patent Publication 2001-288269, Japanese Laid-Open Patent Publication 11-222554 bulletin etc. using well known method.
Such as, by the way that weight average molecular weight is less than or equal to 10000, preferably smaller than it is equal to 5000, more preferably less than or equal to 3000, end is hydroxyl, amino, or the hydrolization groups such as alkoxy, replace the dimethyl polysiloxane of (modification) to intersect agent (graft-linking agent) with the grafting being generally known with the part such as methacryloxypropyl as needed to be used together, water is added, surfactant etc., using high-pressure homogenizer etc. mechanically forced emulsification to reach desired partial size, the emulsion polymerization of polysiloxane can be carried out by becoming acid state and emulsion dispersion in water.
Intersect agent using grafting in the polymerization of polysiloxane used in the present invention, crosslinking agent also can be used as needed.
Grafting, which intersects agent, can be used generally known compound, but it is preferable to use the silane compounds containing vinyl-based polymerizable group of 2 functions.Using the occasion for the silane compound containing vinyl-based polymerizable group for being more than or equal to 3 functions, the impact resistance of final form formed body is likely to decrease.Intersect the concrete example of agent as grafting, for example, gamma-methyl allyl acyloxypropyl dimethoxymethylsilane, gamma-methyl allyl acyloxypropyl diethoxymethylsilane, γ-acryloxypropyl dimethoxymethylsilane, 3- mercapto hydroxypropyl methyl dimethoxysilane etc. can be enumerated.The grafting intersects the use ratio of agent, is preferably 0.1~10 weight %, more preferable 0.5~7 weight %, particularly preferably 1~5 weight % relative to organosiloxane.When the usage amount that grafting intersects agent is greater than 10 weight %, anti-flammability, the impact resistance of final molding body are reduced, and when the usage amount that grafting intersects agent is lower than 0.1 weight %, the mouldability of final molding body is likely to decrease.
When polysiloxane (A) used in the synthesis present invention, if necessary to which crosslinking agent can also be added.As this crosslinking agent, such as, methyltrimethoxysilane can be enumerated, phenyltrimethoxysila,e, the 3 functionality crosslinking agent such as ethyl triethoxysilane, tetraethoxysilane, 1, bis- [2- (dimethoxy-methyl silicyl) ethyl] benzene of 3-, 1, bis- [2- (dimethoxy-methyl silicyl) ethyl] benzene of 4-, 1, bis- [1- (dimethoxy-methyl silicyl) ethyl] benzene of 3-, 1, bis- [1- (dimethoxy-methyl silicyl) ethyl] benzene of 4-, 1- [1- (dimethoxy-methyl silicyl) ethyl] -3- [2- (dimethoxy-methyl silicyl) ethyl] benzene, the 4 functionality crosslinking agents such as 1- [1- (dimethoxy-methyl silicyl) ethyl] -4- [2- (dimethoxy-methyl silicyl) ethyl] benzene.These crosslinking agents can be used alone, or by 2 kinds or a variety of be used in mixed way.The additive amount of the crosslinking agent is preferably used less than relative to polysiloxane (A) equal to 10 weight %, more preferably using less than or equal to 3.0 weight %.When greater than 10 weight %, due to damaging the flexibility of polysiloxane (A), therefore the impact resistance of final molding body is likely to decrease.
In above-mentioned emulsion polymerization, the emulsifier for not losing emulsifying capacity under acid state can be used.As concrete example, alkyl benzene sulphonate, sodium alkyl benzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate, (two) sodium alkylsulfosuccinates, ethylene nonyl phenyl ether sodium sulfonate, sodium alkyl sulfate etc. can be enumerated.These, which can be used alone, can also use 2 kinds or multiple combinations.Wherein, consider from the higher viewpoint of the emulsion stability of lotion, optimizing alkyl benzene sulfonic acid, sodium alkyl benzene sulfonate, alkyl sulfonic acid, sodium alkyl sulfonate, (two) sodium alkylsulfosuccinates.In addition, alkyl benzene sulphonate is also used as the polymerization catalyst of polysiloxane forming component to play a role with alkyl sulfonic acid.
Acid state can be modulated by adding inorganic acids, the organic acids such as alkyl benzene sulphonate, alkyl sulfonic acid, trifluoroacetic acid such as sulfuric acid, hydrochloric acid into system.From the aspect of never corroding production equipment and can get appropriate polymerization speed, preferably pH is adjusted to 1~3, is more preferably adjusted to 1.0~2.5.
From the aspect of available appropriate polymerization speed, polymerization temperature is preferably greater than or equal to 0 DEG C, is more preferably greater than equal to 15 DEG C, is especially preferred more than equal to 25 DEG C.Additionally, it is preferred that being less than or equal to 100 DEG C, more preferably less than or equal to 70 DEG C, particularly preferably less than it is equal to 50 DEG C.Production efficiency reduces when polymerization temperature is lower than 0 DEG C, and there are the increased tendencies of volatile siloxane without preferred when higher than 100 DEG C.
Since the generation reaction of the polysiloxane under acid condition is balanced reaction, therefore it is preferred that after polymerization in acid condition, according to need near room temperature cure more than a few hours make polysiloxane molecular weight after, it is neutralized by aqueous alkalis such as addition sodium hydroxide, potassium hydroxide, sodium carbonate so that the pH of system is 5~8, to make polymerization, stabilize siloxane chain.
Preferably 0.008~0.6 μm, more preferably 0.01~0.4 μm of the average grain diameter of the polysiloxane (A) of latex state.Often difficult to stably obtain polysiloxane of the average grain diameter less than 0.008 μm, anti-flammability, the impact resistance of final molding body are possible to be deteriorated without preferred when average grain diameter is greater than 0.6 μm.
Vinyl monomer (D) contains 100~50 weight % of multi-functional monomer (B), preferably 100~80 weight % and other copolymerizable monomers (C) 0~50 weight %, preferably 0~20 weight % more than or equal to 2 polyunsaturated bonds by intramolecular and forms.When the amount of multi-functional monomer (B) is very little or when the amount of copolymerizable monomer (C) is too many, the tendency that the anti-flammability and impact resistance improvement that there is finally obtained graft copolymer reduce is without preferred.
Concrete example as multi-functional monomer (B), allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, dially phthalate, two (methacrylic acid) glycol esters, two (methacrylic acid) 1,3-BDO esters, divinylbenzene etc. can be enumerated.These, which can be used alone, by 2 kinds or a variety of can also be used in combination.Wherein, allyl methacrylate is particularly preferably used from the aspect of economy and effect.
Amount using vinyl monomer (D) is 0~10 parts by weight, preferably 0.1~10 parts by weight, more preferably 0.5~5 parts by weight, and greater than the occasion of 10 parts by weight, there are anti-flammabilitys and the tendency of impact resistance reduction without preferred.
, it is preferable to use vinyl monomer (D) in terms of flame-retarded effect and aesthetic appearance raising.
Using the straight-chain siloxanes of high molecular weight as the occasion of raw material, unevenly enter intramolecular due to intersecting agent as the grafting with the reflecting point of vinyl monomer, therefore with using low molecular annular siloxane compared with the occasion of raw material, the amount for being coated in the vinyl monomer (E) on polysiloxane particle (A) is reduced, there is the tendency for being compounded into the poor fire of final molding body obtained in thermoplastic resin in its result, but by using to contain the multi-functional monomer vinyl monomer as main component (D) more than or equal to 2 unsaturated bonds, insufficient reflecting point can be supplemented, the anti-flammability and aesthetic appearance of final molding body can be improved.
Concrete example as copolymerizable monomer (C), such as styrene can be enumerated, α-methylstyrene, p-methylstyrene, to the aromatic vinyls base class monomer such as butylstyrene, acrylonitrile, the vinyl cyanides class monomer such as methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid-2-ethyl caproite, glycidyl acrylate, hydroxy-ethyl acrylate, hy-droxybutyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate etc. (methyl) acrylic ester monomer, itaconic acid, (methyl) acrylic acid, fumaric acid, the vinyl monomer etc. containing carboxyl such as maleic acid.These can be used alone, and by 2 kinds or a variety of can also be used in combination.
Vinyl monomer used in the present invention (E) is the compatibility in order to ensure graft copolymer and thermoplastic resin, is evenly dispersed in graft copolymer in thermoplastic resin and the ingredient that uses.As specific monomer, can enumerate and other identical monomers of copolymerizable monomer (C) in above-mentioned vinyl monomer (D).As concrete example, such as styrene can be enumerated, α-methylstyrene, p-methylstyrene, to the aromatic vinyls base class monomer such as butylstyrene, acrylonitrile, the vinyl cyanides class monomer such as methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid-2-ethyl caproite, glycidyl acrylate, hydroxy-ethyl acrylate, hy-droxybutyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate etc. (methyl) acrylic ester monomer, itaconic acid, (methyl) acrylic acid, fumaric acid, the vinyl monomer etc. containing carboxyl such as maleic acid.These can be used alone, and can also be used in combination two or more.The usage amount of vinyl monomer (E) is 5~70 parts by weight, preferably 5~45 parts by weight.The occasion, organopolysiloxane (A) preferably 55~95 parts by weight.
Preferably using free radical polymerization in the polymerizeing of the vinyl monomer (D) being used in the present invention and vinyl monomer (E).In addition, vinyl monomer (D) can polymerize with vinyl monomer (E) using 1 section, 2 sections or multi-stage polymeric can also be used.
Above-mentioned vinyl monomer is also polymerize, but in order to ensure the compatibility with thermoplastic resin not only on the surface of polysiloxane particle in inside particles, preferably as far as possible to be polymerize on the surface of the particle on a small quantity.However, increasing in the ratio of inside particles vinyl monomer polymerization, the anti-flammability of finally obtained formed body reduces when using the high radical initiator of hydrophobicity.Therefore the occasion for intersecting agent using above-mentioned grafting can reduce the amount in the vinyl monomer of inside particles polymerization, the ratio polymerizeing in particle surface be improved, so that anti-flammability be made to improve by selectively using the radical initiator relatively high to the dissolubility of water.
Concrete example as radical initiator (F), the organic peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, t-butylperoxyisopropyl carbonic ester, di-t-butyl peroxide, the peroxylauric acid tert-butyl ester, lauroyl peroxide, succinic acid peroxide, cyclohexanone peroxide, diacetone peroxide, hydroperoxidation terpane can be enumerated, the inorganic peroxides such as potassium peroxydisulfate, ammonium persulfate, 2,2 '-azodiisobutyronitriles, 2,2 '-azos two -2, azo-compounds such as 4- methyl pentane nitrile etc..Wherein, from reactive high consideration, the preferably peroxide compounds such as organic peroxide or inorganic peroxide.Wherein, more preferably have with hydroperoxidation terpane, cumene hydroperoxide is same or higher water-soluble peroxide.
, it is preferable to use being more than or equal to the radical initiator of 0.5g/100g (20 DEG C), preferably 1~16g/100g (20 DEG C) to the dissolubility of water in radical initiator (F).In thermoplastic resin there is the tendency that the anti-flammability of final formed body obtained improves using the occasion of copolymer made from such initiator in compounding.
Be more than or equal to the concrete example of the radical initiator (F) of 0.5g/100g (20 DEG C) as the dissolubility to water, such as the tertiary hexyl of hydroperoxidation terpane, t-butyl hydroperoxide, potassium peroxydisulfate, cumene hydroperoxide, hydroperoxidation can be enumerated etc..These can be used alone, and by 2 kinds or a variety of can also be used in combination.
The usage amount of radical initiator can use in range well known to those skilled in the art.
When carrying out the polymerization in the redox systems such as ferrous sulfate-formaldehyde sodium sulfoxylate-ethylenediamine tetra-acetic acid 2Na salt, ferrous sulfate-glucose-sodium pyrophosphate, ferrous sulfate-sodium pyrophosphate-sodium phosphate, due to can also complete to polymerize under low polymerization temperature, preferably.
It as the method for the isolating polymer from the graft copolymer latex as made from emulsion polymerization, such as can enumerate by adding the metal salts such as calcium chloride, magnesium chloride, magnesium sulfate into latex, by latex condensation, separation, washing, dehydration, dry method etc..Spray drying process can also be used.
Graft copolymer obtained in this way is used as fire retardant, and the excellent fire retardant resin composition of anti-flammability, impact resistance can be made by being compounded in various thermoplastic resins.
As above-mentioned thermoplastic resin, from the aspect of it can get good anti-flammability, preferably containing the polycarbonate resin more than or equal to 50 weight % polycarbonate.Preferred concrete example as polycarbonate resin, polycarbonate can be used, the polycarbonate/polyesters hybrid resin such as polycarbonate/polyethylene terephthalate hybrid resin and polycarbonate/polybutylene terephthalate (PBT) hybrid resin, polycarbonate/acrylonitrile-styrol copolymer hybrid resin, polycarbonate/butadiene-styrene copolymer (HIPS resin) hybrid resin, polycarbonate/acrylonitrile-butadiene rubber-styrene copolymer (ABS resin) hybrid resin, polycarbonate/acrylonitrile-butadiene rubber-α-methylstyrenecopolymer hybrid resin, polycarbonate/SBR styrene butadiene rubbers-acrylonitrile-N-phenylmaleimide copolymer hybrid resin, polycarbonate/acrylonitrile-acrylic rubber-styrenic copolymer (AAS resin) hybrid resin Deng.
Additive amount as the above-mentioned graft copolymer containing polysiloxane relative to thermoplastic resin is preferably compounded 0.1~20 parts by weight of graft copolymer, more preferable 0.1~10 parts by weight relative to 100 parts by weight of thermoplastic resin from the aspect of anti-flammability.When lower than 0.1 parts by weight final molding body anti-flammability difficulty improve, and be greater than 20 parts by weight when formed body mouldability (especially mobility) be possible to be greatly reduced without preferred.
By having carried out condensation from latex, heat treatment, being dehydrated, the mixing for the fire retardant powder and thermoplastic resin that the dry graft copolymer containing polysiloxane is constituted, after being mixed by using Henschel kneading machine, ribbon mixer etc., melting mixing is carried out using roller, extruder, kneader etc. and is mixed.
At this point it is possible to add usually used compounding agent, i.e. antioxidant, anti-sag agent, polymer processing aid, fire retardant, impact resistance improver, plasticizer, lubricant, ultraviolet absorbing agent, pigment, glass fibre, filler, polymeric lubricant etc..
As the method for forming of fire retardant resin composition, the method for forming used in the molding of common thermoplastic resin composition can be used, that is, injection moulding, extrusion moulding, blow molding method, rolling-molding method etc..
Molded product obtained becomes the product of impact resistance and excellent in flame retardance.
Embodiment
The present invention is concretely demonstrated according to embodiment, but the present invention is not only defined in these embodiments.Furthermore measurement and the test progress as described below in embodiment below and comparative example.
[polymerisation conversion]
Solid content was found out by latex dry 1 hour using 120 DEG C of hot-air driers, is calculated by 100 × solid content/addition amount of monomer (%).
[volume average particle size]
The volume average particle size of seed polymer, polysiloxane particle and graft copolymer is measured in the state of latex.The MICROTRAC UPA that LEED&NORTHRUP INSTRUMENTS corporation is used as measurement device, using light scattering determining volume average particle size (μm).
[volatile siloxane containing ratio]
It is found out using gas-chromatography (GC) parsing.Methyl ethyl ketone is added into latex, resin grout liquid or powder to be stripped, and adds octamethyltrisiloxane as internal standard.Using column: SiliconeDC-550 is filled with φ 3mm × 3m of 20 weight % Network ロ モ ソ Le Block WNAW#60-80, is implemented with gas-chromatography GC-14B ((strain) Shimadzu manufactures made).Analysis four cyclosiloxane of prestox (D4), decamethylcyclopentaandoxane (D5), ten diformazan basic rings, six siloxanes (D6) amount are found out, using these total amount relative to resin solid content ratio as volatile siloxane containing ratio.
[impact resistance]
It is evaluated using band 1/8 inch of stick of notch by the izod test at 0 DEG C according to ASTM D-256.
[anti-flammability]
It is evaluated by UL94 V test.
[aesthetic appearance]
The size of the surface roughness features generated with the gate portions of formed body is evaluated.
Zero: rough surface area is less than 1cm2
×: rough surface area is more than or equal to 1cm2
(Production Example 1)
It will be by 200 parts by weight of pure water, 1 parts by weight of neopelex (SDBS), 1 parts by weight of dodecyl benzene sulfonic acid (DBSA), terminal hydroxy group organopolysiloxane (chemical industry Co., Ltd, DHPDMS SHIN-ETSU HANTOTAI trade name: PRX413) 100 parts by weight that cyclic low molecular weight content of siloxane of the silicon atom number less than or equal to 10 is 0.7 weight %, the mixed liquor of 5 parts by weight of gamma-methyl allyl acyloxypropyl methyl dimethoxysilane (DSMA) composition is stirred after five minutes at 10000rpm using homomixer, silicone emulsion is prepared by 3 times in high-pressure homogenizer under the pressure of 500bar.The silicone emulsion is promptly once added in five mouthfuls of flasks with the additional mouth of reflux condenser, nitrogen mouth blown, monomer, thermometer.It is reacted 6 hours at 30 DEG C in the system of stirring.Then, after being cooled to 23 DEG C of placements 20 hours, make the pH of system terminate to polymerize back to 6.8 using sodium hydroxide, obtain the latex of particle containing polysiloxane (SR-1).The aggregate rate of polyorganosiloxane latex obtained is 96 polymerization %, and volatile siloxane containing ratio is 4.4%, and volume average particle size is 0.28 μm.
(Production Example 2)
Other than it will be grafted intersection agent and be changed to mercapto dimethylamine oxygroup methyl-monosilane (MPrDMS), it is carried out similarly synthesis with Production Example 1, the latex of particle containing polyorganosiloxane latex (SR-2) is made.The aggregate rate of polyorganosiloxane latex obtained is 96 polymerization %, and volatile siloxane containing ratio is 4.1%, and volume average particle size is 0.28 μm.
(Production Example 3)
At the mixture being grouped as 5 minutes preparation lotions will be stirred at 7000rpm using homomixer by 300 parts by weight of pure water, 0.5 parts by weight (solid component) of neopelex (SDBS), 100 parts by weight of octamethylcy-clotetrasiloxane (D4), 5 parts by weight of gamma-methyl allyl acyloxypropyl methyl dimethoxysilane (DSMA).The silicone emulsion is promptly once added to and is added in five mouthfuls of flasks of mouth, thermometer with reflux condenser, nitrogen mouth blown, monomer.
Then, 10% dodecyl benzene sulfonic acid aqueous solution, 1 parts by weight (solid component) is added, is warming up to 80 DEG C under nitrogen flowing while stirring.25 DEG C are cooled to after continuing stirring at 80 DEG C 15 hours to place 30 hours.Then so that pH is become 6.5 with sodium hydroxide terminates to polymerize, be made polyorganosiloxane latex (SR-3).The aggregate rate of polyorganosiloxane latex obtained is 85 polymerization %, and volatile siloxane containing ratio is 15%, and volume average particle size is 0.20 μm.
(Production Example 4)
Other than it will be grafted intersection agent and be changed to mercapto dimethylamine oxygroup methyl-monosilane (MPrDMS), it is carried out similarly synthesis with Production Example 3, the latex of particle containing polyorganosiloxane latex (SR-4) is made.The aggregate rate of polyorganosiloxane latex obtained is 86 polymerization %, and volatile siloxane containing ratio is 14%, and volume average particle size is 0.18 μm.
(embodiment 1~12, comparative example 1~6)
Into five mouthfuls of flasks with blender, reflux condenser, nitrogen mouth blown, the additional mouth of monomer and thermometer, polysiloxane particle 70 or 80 parts by weight (solid component) made from Production Example 1~4 are added with latex state, are warming up to 60 DEG C under nitrogen flowing while stirring.After reaching 60 DEG C, after adding formaldehyde sodium sulfoxylate (SFS) 0.13 parts by weight, 0.004 parts by weight of disodium ethylene diamine tetraacetate (EDTA), 0.001 parts by weight of ferrous sulfate, it is disposably added after allyl methacrylate (ALMA) is mixed with radical initiator RY-0~4 shown in table 1 by parts by weight shown in table 2, continuation is stirred 1 hour at 60 DEG C.Then, dropwise addition addition is carried out after 30 or 20 parts by weight of methyl methacrylate (MMA) being mixed with radical initiator RY-0~4 shown in table 1 by parts by weight shown in table 2, continues to stir obtained graft copolymer latex after additional.The aggregate rate, volatile siloxane containing ratio and volume average particle size of graft copolymer latex obtained are shown in table 2.Then, latex is diluted with pure water, after making solid component concentration 15%, is added 2.5% calcium chloride water, 4 parts by weight (solid component), obtain condensation slurries.After condensation slurries are heated to 95 DEG C, after being cooled to 50 DEG C of dehydrations, the powder (SG-1~11) of obtained poly organo siloxane graft copolymer is dried.
Furthermore, graft copolymer latex shown in ratio example 1~6, using have selected from hydroxyl, amino, hydrolization group end group straight-chain or branched siloxanes, but use annular siloxane, it is known that the volatile siloxane containing ratio of graft copolymer latex obtained is big.
(embodiment 13~24, comparative example 7~9)
Use polycarbonate resin (Supreme Being people is melted into Co., Ltd's system, trade name: パ Application ラ イ ト L1225WX) and as the powder of poly organo siloxane graft copolymer obtained in the polytetrafluoroethylene (PTFE) (Daikin Industries Co., Ltd system, trade name: Port リ Off ロ Application FA-500) and table 2 of anti-sag agent, is compounded by composition shown in table 3.
Blend obtained is used double screw extruder (Japanese Zhi Gang Co., Ltd TEX44SS) melting mixing, granulation at 270 DEG C.1/20 inch of anti-flammability evaluation test piece and 1/8 inch of impact resistance evaluation test piece is made in the FAS100B injection moulding machining for the FANUC Co., Ltd that pellet obtained is set in 280 DEG C using barrel temperature.It is evaluated using test piece obtained according to above-mentioned evaluation method.The anti-flammability of formed body, impact resistance evaluation result is shown in table 3.
Table 1
| Radical initiator No. | To the dissolubility (g/100g water) of 20 DEG C of water | Molecular weight | |
| Hydroperoxidation terpane | RY-0 | 1.6 | 172 |
| T-butyl hydroperoxide | RY-1 | 15.7 | 90 |
| Cumene hydroperoxide | RY-2 | 1.6 | 152 |
| T-butylperoxyisopropyl monocarbonate | RY-3 | 0.02 | 176 |
| Tert-hexyl peroxide isopropyl monocarbonate | RY-4 | 0.01 | 204 |
Table 2
| Embodiment | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | ||
| Polysiloxane particle (A) (part) | SR-1 SR-2 SR-3 SR-4 | 80 - - - | 80 - - - | 80 - - - | - 80 - - | - 80 - - | - 80 - - | 70 - - - | 70 - - - | 70 - - - |
| Vinyl monomer (D) (part) | ALMA | 1.5 | 1.5 | 15 | 4.5 | 4.5 | 4.5 | 1 | 1.5 | 2 |
| Radical initiator (part) | RY-0 RY-1 RY-2 RY-3 RY-4 | - 0.03 - - - | - 0.015 0.025 - - | - - 0.05 - - | - 0.09 - - - | - 0.045 0.075 - - | - - 0.15 - - | 0.038 - - - - | 0.057 - - - - | 0.076 - - - - |
| Aggregate rate (%) | 99 | 99 | 99 | 99 | 99 | 99 | 99 | 99 | 99 | |
| Vinyl monomer (E) (part) | MMA | 20 | 20 | 20 | 20 | 20 | 20 | 30 | 30 | 30 |
| Radical initiator (part) | RY-0 RY-1 RY-2 RY-3 RY-4 | - 0.039 - - - | - 0.02 0.033 - - | - - 0.066 - - | - 0.039 - - - | - 0.02 0.033 - - | - - 0.066 - - | 0.0229 - - - - | 0.0229 - - - - | 0.0229 - - - - |
| Mixing time after additional time+addition | 1+1 | 1.5+3 | ||||||||
| Aggregate rate (%) | 99 | 99 | 99 | 99 | 99 | 99 | 99 | 99 | 99 | |
| Volatile siloxane amount | 2.5% | 2.5% | 2.5% | 3.0% | 3.0% | 3.0% | 3.0% | 3.0% | 3.0% | |
| Partial size (μm) | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | 0.28 | |
| Graft copolymer No. | SG-1 | SG-2 | SG-3 | SG-4 | SG-5 | SG-6 | SG-1-1 | SG-1-2 | SG-1-3 | |
| Embodiment | Comparative example | |||||||||
| 10 | 11 | 12 | 1 | 2 | 3 | 4 | 5 | 6 | ||
| Polysiloxane particle (A) (part) | SR-1 SR-2 SR-3 SR-4 | 80 - - - | 80 - - - | - 80 - - | - - 80 - | - - 80 - | - - - 80 | - - - 80 | - - - 70 | - - - 70 |
| Vinyl monomer (D) (part) | ALMA | 1.5 | 1.5 | 4.5 | 1.5 | 1.5 | 4.5 | 4.5 | 1.5 | 3 |
| Radical initiator (part) | RY-0 RY-1 RY-2 RY-3 RY-4 | - - - 0.057 - | - - - - 0.066 | - - - 0.171 - | - 0.03 - - - | - - 0.05 - - | - 0.03 - - - | - - 0.05 - - | 0.057 - - - - | 0.114 - - - - |
| Aggregate rate (%) | 99 | 99 | 99 | 99 | 99 | 99 | 99 | 99 | 99 | |
| Vinyl monomer (E) (part) | MMA | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 30 | 30 |
| Radical initiator (part) | RY-0 RY-1 RY-2 RY-3 RY-4 | - - - 0.077 - | - - - - 0.089 | - - - 0.077 - | - 0.039 - - - | - - 0.066 - - | - 0.039 - - - | - - 0.066 - - | 0.0229 - - - - | 0.0229 - - - - |
| Mixing time after additional time+addition | 1+1 | 1.5+3 | ||||||||
| Aggregate rate (%) | 99 | 99 | 99 | 99 | 99 | 99 | 99 | 99 | 99 | |
| Volatile siloxane amount | 2.5% | 2.5% | 3.0% | 11% | 11% | 10% | 10% | 10% | 10% | |
| Partial size (μm) | 0.28 | 0.28 | 0.28 | 0.2 | 0.2 | 0.18 | 0.18 | 0.25 | 0.25 | |
| Graft copolymer No. | SG-7 | SG-8 | SG-9 | - | - | - | - | SG-10 | SG-11 | |
Table 3
| Embodiment | ||||||||||
| 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | ||
| Thermoplastic resin (part) | PC | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Graft copolymer (part) | SG-1 SG-1-1 SG-1-2 SG-1-3 SG-2 SG-3 SG-4 SG-5 SG-6 | 3 - - - - - - - - | - - - - 3 - - - - | - - - - - 3 - - - | - - - - - - 3 - - | - - - - - - - 3 - | - - - - - - - - 3 | - 3 - - - - - - - | - - 3 - - - - - - | - - - 3 - - - - - |
| Anti-sag agent (part) | PTFE | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Formed body appearance | - | - | - | - | - | - | ○ | ○ | ○ | |
| 1/20 inch formed body of anti-flammability | Total burning number of seconds (second) determines whether trickling | 69 without V-1 | 58 without V-1 | 80 without V-1 | 116 without V-1 | 60 without V-1 | 124 without V-1 | 100 without V-1 | 69 without V-1 | 92 without V-1 |
| 1/8 inch of IZOD intensity of impact resistance | 0℃(kJ/m2) | 52 | 45 | 34 | 63 | 54 | 41 | 37 | 35 | 35 |
| Embodiment | Comparative example | |||||||||
| 22 | 23 | 24 | 7 | 8 | 9 | |||||
| Thermoplastic resin (part) | PC | 100 | 100 | 100 | 100 | 100 | 100 | |||
| Graft copolymer (part) | SG-7 SG-8 SG-9 SG-10 SG-11 | 3 - - - - | - 3 - - - | - - 3 - - | - - - - - | - - - 3 - | - - - - 3 | |||
| Anti-sag agent (part) | PTFE | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |||
| Formed body appearance | - | - | - | - | ○ | ○ | ||||
| 1/20 inch formed body of anti-flammability | Total burning number of seconds (second) determines whether trickling | 150 without V--1 | 176 without V-1 | 168 without Not-V | 190 have Not-V | 136 without V-1 | 144 have V-1 | |||
| 1/8 inch of IZOD intensity of impact resistance | 0℃(kJ/m2) | 30 | 30 | 36 | 12 | 25 | 20 | |||
Purposes as the molded product as made from fire retardant resin composition of the invention, the purposes of the special requirement anti-flammability such as component or shell for being not particularly limited, such as desktop computer, notebook computer, tower computer, server-type computer, printer, duplicator can be enumerated etc..
Claims (6)
1. the graft copolymer containing polysiloxane, it is prepared as follows: by that will have selected from hydroxyl, amino, in the presence of 30~95 parts by weight of polysiloxane (A) of latex state prepared by the straight-chain or branched silicone emulsion polymerization of the end group of hydrolization group, by 0~10 weight parts of polymer of vinyl monomer (D) by being formed containing 100~50 weight % of multi-functional monomer (B) and 0~50 weight % of other copolymerizable monomers (C) more than or equal to 2 polyunsaturated bonds, in turn by 5~70 parts by weight ((A) of vinyl monomer (E), (D), (E) add up to 100 parts by weight) polymerization.
2. the graft copolymer described in claim 1 containing polysiloxane, wherein vinyl monomer (D) is 0.1~10 parts by weight.
3. the graft copolymer of any of claims 1 or 2 containing polysiloxane, it is characterized by: the use of the dissolubility to water being the radical initiator (F) more than or equal to 0.5g/100g (20 DEG C) when the polymerization of (D) and/or (E).
4. the described in any item graft copolymers containing polysiloxane of claims 1 to 3, wherein, vinyl monomer (E) is at least one kind of monomer for being selected from aromatic vinyl base class monomer, vinyl cyanide class monomer, (methyl) acrylic ester monomer and the vinyl monomer containing carboxyl.
5. the fire retardant being made of the described in any item graft copolymers containing polysiloxane of Claims 1 to 4.
6. resin combination, wherein relative to 100 parts by weight of thermoplastic resin, be compounded 0.1~20 parts by weight of fire retardant described in claim 5 and form.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP048785/2004 | 2004-02-24 | ||
| JP2004048786 | 2004-02-24 | ||
| JP048786/2004 | 2004-02-24 |
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| Publication Number | Publication Date |
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| CN1922228A true CN1922228A (en) | 2007-02-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316160A (en) * | 2021-11-17 | 2022-04-12 | 科思创树脂制造(佛山)有限公司 | Acrylic emulsion polymer and preparation method of water-based paint based on polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316160A (en) * | 2021-11-17 | 2022-04-12 | 科思创树脂制造(佛山)有限公司 | Acrylic emulsion polymer and preparation method of water-based paint based on polymer |
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