JP2004307841A - Rubber-modified styrenic resin excellent in weather resistance and impact resistance, its production process and laminate obtained by using the resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber-modified styrenic resin excellent in weather resistance and impact resistance, its production process and a laminate obtained by using the resin and excellent in weather resistance and adhesion strength. <P>SOLUTION: This rubber-modified styrenic resin is obtained by the production process of polymerizing a partially hydrogenated rubber obtained by hydrogenation of a conjugated diene-based rubber, a styrenic monomer and a (meth)acrylate-based monomer using a radical initiator by bulk polymerization or solution polymerization under agitation, so that the methyl ethyl ketone-insoluble gel fraction of the obtained rubber-modified styrenic resin and the swelling index of the gel content each falls within a specific range. The laminate is obtained by using the resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a rubber-modified styrenic resin having excellent weather resistance and impact resistance, a method for producing the same, and a laminate using the resin.

Rubber-modified styrene resin represented by impact-resistant polystyrene (HIPS, high-impact polystyrene) is a resin excellent in impact resistance, moldability, and dimensional stability. It is used in various fields as a molding material and packaging material.
However, as is well known, conventional rubber-modified styrenic resins contain unsaturated double bonds in the molecular chains of rubber particles dispersed in polystyrene in the continuous phase, and are therefore degraded by ultraviolet light or oxygen in the air. However, there is a problem that the weather resistance is low, such as discoloration and a decrease in impact resistance. Therefore, it has hardly been used in applications requiring weather resistance, for example, outdoors.

In addition, polymethyl methacrylate resin or resin containing methyl methacrylate as a main component is used in a wide range of fields such as automobile parts, electric parts, lighting equipment and displays because of its excellent transparency, gloss and weather resistance. However, its impact strength is low and its use is limited.
In addition, the continuous phase is a copolymer obtained by polymerizing styrene, butyl acrylate, and methyl methacrylate, and the rubbery polymer contained in the dispersed particles is a styrene-butadiene block copolymer. Although a method of matching is known, similar to rubber-modified styrenic resins, since rubber particles contain unsaturated double bonds in the molecular chain, they are degraded by ultraviolet light or oxygen in the air, causing discoloration and impact resistance. And there is a problem that the weather resistance is low.

Also, ethylene-α-olefin copolymer rubbers (EPM, EPDM), acrylic rubbers and the like are used as rubber components, and styrene and acrylonitrile are graft-polymerized. It is known that, compared to rubber-modified styrenic resins, they have higher resistance to ultraviolet rays and oxygen in the air and have better weather resistance.
However, the AES resin and the ASA resin have disadvantages of being inferior in colorability and moldability as compared with the rubber-modified styrene resin. In particular, with respect to the coloring properties, compared to the rubber-modified styrenic resin, the depth is insufficient in a dark color, and a large amount of a coloring agent is required to achieve the same color tone.
Patent Literature 1 discloses an impact-resistant styrene resin containing a partially hydrogenated conjugated diene-based rubber as a toughening agent and having excellent impact resistance and rigidity, but mentions weather resistance as an effect. Absent.

  Patent Document 2 discloses a production method in which a monomer having methyl methacrylate as a main component is graft-polymerized to a rubbery polymer obtained by hydrogenating a block copolymer comprising an aromatic vinyl and a conjugated diene compound. However, since the hydrogenation rate of the block copolymer is high and the number of double bonds in the rubber decreases, the crosslinking reaction of the rubber component becomes extremely difficult to proceed. Is formed, the particles are deformed or broken by the mechanical shearing force applied during extrusion or injection molding, resulting in reduced strength and poor surface gloss and transparency of the molded product. Patent Document 2 does not disclose any technology relating to crosslinking of rubber components, including Examples.

On the other hand, a method of laminating a resin having excellent weather resistance on the surface layer side of the thermoplastic resin in order to overcome the problem of weather resistance of a thermoplastic resin such as a styrene resin and a vinyl chloride resin and to enable use outdoors. In particular, polystyrene and impact-resistant polystyrene have poor affinity with methacrylic resin, AAS resin, and AES resin, which are typical resins having excellent weather resistance, and are strongly bonded by heat fusion such as co-extrusion. It was not possible to form a bonded laminate.
Patent Document 3 discloses that a radically polymerizable monomer component is graft-copolymerized in the presence of a hydrogenated diene polymer obtained by hydrogenating a diene polymer composed of an aromatic vinyl compound and a conjugated diene. A laminate of a rubber-reinforced resin having a specific range of graft ratio and an intrinsic viscosity of methyl ethyl ketone-soluble component and another thermoplastic resin and Patent Document 4 disclose aromatic vinyl in the presence of a hydride of a conjugated diene-based rubbery polymer. A laminate of a styrene resin and another thermoplastic resin obtained by polymerizing a compound or another vinyl monomer copolymerizable with an aromatic vinyl compound and an aromatic vinyl compound is disclosed, but a styrene resin, It is difficult to adhere to both vinyl chloride resins, and in particular, the adhesion to polystyrene and high-impact polystyrene is insufficient, and the adhesive strength has not yet reached a practical level. Further, it has the same disadvantages due to the high hydrogenation rate of the diene polymer ahead.

JP-A-64-90208 JP-A-1-163209 Japanese Patent No. 2946627 JP-A-9-76426

  The present invention provides a rubber-modified styrene-based resin having excellent weather resistance, excellent impact resistance, and similar coloring properties and processability to a conventional rubber-modified styrene-based resin, and a method for producing the same, and the resin. An object of the present invention is to provide a laminate excellent in weather resistance and adhesive strength.

  The present inventors have sincerely studied to solve such a current problem, and as a result, have found that a partially hydrogenated rubber obtained by hydrogenating a conjugated diene rubber, a styrene monomer and a (meth) acrylate ester The monomer is subjected to bulk polymerization or solution polymerization with stirring using a radical initiator, and the resulting rubber-modified styrene-based resin has a methyl ethyl ketone insoluble content gel fraction and a swelling index of the gel content for toluene within a specific range. The present inventors have found that the above problems can be solved by forming a laminate using a rubber-modified styrenic resin obtained by a production method of polymerizing so as to obtain a resin and the resin, and have completed the present invention.

That is, the present invention provides a partially hydrogenated rubber (A) in which 7 to 70 mol% of the unsaturated units of the conjugated diene rubber is hydrogenated, a styrene monomer (B), and a (meth) acrylate ester rubber. The monomer (C) is (A) + (B) + (C) as 100 parts by weight, (A) is 3 to 16 parts by weight, and the weight ratio of (B) / (C) is 20/80. In the range of ~ 82/18, bulk polymerization or solution polymerization is carried out with stirring using a radical initiator, and the resulting rubber-modified styrene resin has a methyl ethyl ketone insoluble gel fraction of 6 to 35% by weight and the gel The present invention relates to a method for producing a rubber-modified styrenic resin, characterized in that polymerization is carried out so that the swelling index of toluene for toluene is 8 to 16. Further, the present invention provides a partially hydrogenated rubber (A) in which 7 to 70 mol% of the unsaturated units of the conjugated diene rubber is hydrogenated, a styrene monomer (B), and a (meth) acrylate ester monomer. Monomer (C) in a weight ratio of (B) / (C) in the range of 20/80 to 82/18 by polymerization using a radical initiator with bulk polymerization or solution polymerization with stirring. Rubber-modified styrenic resin comprising a dispersed rubber particle phase and a resin phase, wherein the styrene-based monomer unit and the (meth) acrylate-based monomer unit are 20 in the copolymer constituting the resin phase. / 80-80 / 20 weight ratio, and the obtained rubber-modified styrenic resin has a methyl ethyl ketone insoluble gel fraction of 6-35 wt% and a swelling index of the gel for toluene of 8-16. Characterized by It relates to a rubber-modified styrenic resin. Further, the present invention provides a partially hydrogenated rubber (A) in which 7 to 70 mol% of the unsaturated units of the conjugated diene rubber is hydrogenated, a styrene monomer (B), and a (meth) acrylate ester monomer. Monomer (C) in a weight ratio of (B) / (C) in the range of 20/80 to 82/18 by polymerization using a radical initiator with bulk polymerization or solution polymerization with stirring. Rubber-modified styrenic resin comprising a dispersed rubber particle phase and a resin phase, wherein the styrene-based monomer unit and the (meth) acrylate-based monomer unit are 20 in the copolymer constituting the resin phase. / 80-80 / 20 weight ratio, and the obtained rubber-modified styrene-based resin has a methyl ethyl ketone insoluble content gel fraction of 6-35 wt% and a swelling index of the gel for toluene of 8-16. Modified polystyrene And a layer made of a layer comprising the system resin (I) (I) other than the styrene-based resin or vinyl chloride resin (II), a laminate, characterized in that it has a laminated structure. The partially hydrogenated rubber (A) preferably has a 5% by weight styrene solution viscosity at 25 ° C. of 20 to 150 centipoise. Further, in the partially hydrogenated rubber (A), the conjugated diene rubber before hydrogenation is preferably polybutadiene. Further, it is preferable that the rubber particle diameter of the dispersed rubber particle phase is 0.5 to 3.5 μm. Further, it is preferable that the styrene monomer (B) is styrene and the (meth) acrylate monomer (C) is methyl methacrylate or methyl methacrylate and butyl acrylate. Further, the layer composed of (I) and (II) may be thermally fused. In the layer composed of (II), the styrene resin other than (I) is preferably at least one selected from polystyrene, impact-resistant polystyrene and ABS resin. Further, the layer made of (II) may be a styrene-based resin other than (I) or a wood powder-containing resin other than vinyl chloride-based resin. Further, the layer composed of (II) may be a foam of a styrene resin or a vinyl chloride resin other than (I). Further, the layer composed of (II) may be recycled polystyrene, impact-resistant polystyrene, ABS resin, vinyl chloride-based resin, and a resin containing wood powder thereof.

  The rubber-modified styrenic resin obtained by the production method of the present invention is a material having excellent weather resistance and impact resistance, and excellent in moldability and coloring. The rubber-modified styrenic resin and the laminate thereof of the present invention can be used in a wide range of applications such as the field of automobiles, household appliances and miscellaneous goods, and the field of housing and building materials including exterior products such as exteriors, and particularly, -It can be suitably used as outdoor products and building materials in the field of building materials.

Hereinafter, the present invention will be described in detail. The partially hydrogenated rubber used in the present invention is obtained by partially hydrogenating a conjugated diene-based polymer obtained by a known method. The conjugated diene polymer obtained by a known method generally includes all rubbers used for producing a rubber-modified styrene resin. Examples include polybutadiene, styrene-butadiene copolymer (random and block SBR), polyisoprene, butadiene-isoprene copolymer, butadiene-isoprene-styrene copolymer, natural rubber, and the like. In particular, polybutadiene is preferably used from the viewpoint of weather resistance and reinforcing effect.
The hydrogenation rate of the conjugated diene polymer is 7 to 70 mol% of the conjugated diene units. Preferably, it is 9 to 60 mol%. More preferably, it is 15 to 45 mol%. If the degree of hydrogenation is less than 7 mol%, the weather resistance will not be improved. On the other hand, if it exceeds 70 mol%, the impact resistance is poor.
As the hydrogenation method, any conventionally known method may be used. For example, a method described in JP-A-52-41890, JP-A-59-133203, and JP-A-60-220147 is used. be able to.

Although not particularly limited, the content of unsaturated 1,2 vinyl bonds after hydrogenation is preferably 15 mol% or less. More preferably, it is at most 10 mol%. If it exceeds 15 mol%, heat resistance and weather resistance are poor.
The partially hydrogenated rubber after partial hydrogenation has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) measured at 100 ° C. of 20 to 80, and a 5% by weight styrene solution viscosity (5% SV) at 25 ° C. ) Is preferably in the range of 20 to 150 centipoise. A more preferred range is 30 to 120 centipoise. It is preferable to use a partially hydrogenated rubber in this range because the rubber composition has excellent impact resistance and can easily control the rubber particle diameter during production.
The content of the partially hydrogenated rubber used in producing the rubber-modified styrenic resin of the present invention is 3 to 16% by weight. Preferably it is 5 to 14% by weight. If it is less than 3% by weight, the reinforcing effect is not sufficient and the impact resistance is insufficient. If the content exceeds 16% by weight, the impact resistance is improved, but the rigidity, moldability, and weather resistance are reduced, and the usage is greatly restricted.

  Examples of the styrene-based monomer used in the present invention include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene and the like, and they may be used alone or in combination of two or more. In particular, styrene is preferably used. Examples of the (meth) acrylate monomer include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. These may be used alone or as a mixture. In particular, methyl methacrylate or a mixture of methyl methacrylate and butyl acrylate can be suitably used. When a mixture of methyl methacrylate and butyl acrylate is used, the amount of butyl acrylate is preferably not more than 10% by weight of the polymer forming the continuous phase. If it exceeds 10% by weight, the heat resistance is lowered, and the practical range of the molded product is undesirably narrowed.

The ratio of the styrene monomer to the (meth) acrylate monomer is 20:80 to 82:18 (weight ratio). Preferably, it is 30:70 to 70:30. More preferably, it is 40:60 to 60:40. If the ratio of the styrene-based monomer is less than 20, a resin satisfying both impact resistance and processability cannot be obtained at the same time. Not preferred. On the other hand, when the ratio of the styrene monomer exceeds 82, the weather resistance decreases, and further, when the laminate is formed, the adhesiveness to a vinyl chloride resin, an ABS resin, or the like decreases, which is not preferable.
When producing the rubber-modified styrenic resin of the present invention, another copolymerizable monomer (D) may be used as necessary. Other copolymerizable monomers used herein include, for example, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, maleimide, N-methyl Monoimide-containing monomers such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; epoxy-containing monomers such as glycidyl acrylate and glycidyl methacrylate; carboxyls such as acrylic acid, methacrylic acid, maleic acid and itaconic acid Group-containing monomer, amino group-containing monomer such as acrylamine, aminoethyl methacrylate, aminopropyl methacrylate, and hydroxyl group-containing such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate Such as the amount thereof and the like.

The molecular weight (molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC)) of the styrene resin forming the resin phase of the present invention is preferably 70,000 to 300,000, more preferably 90,000 in terms of weight average molecular weight. The range is ~ 200,000.
The rubber particle diameter of the dispersed rubber particle phase of the present invention is preferably in the range of 0.5 to 3.5 μm. More preferably, it is 0.7 to 3.0 μm. More preferably, it is 1.0 to 3.0 μm. If it is less than 0.5 μm, the reinforcing effect is not sufficient, and the impact resistance is insufficient. If it exceeds 3.5 μm, the rigidity is undesirably reduced.
In the present invention, a partially hydrogenated rubber is used as the rubber component. The stability of the rubber itself against light, etc., that is, the weather resistance, improves as the hydrogenation rate increases, but the chemical reaction sharply decreases with the increase in the hydrogenation rate. It will be difficult to progress. The rubber-modified styrene-based resin of the present invention is characterized in that a copolymer of a styrene-based monomer and a (meth) acrylate-based monomer in a specific composition range is grafted on a rubber particle surface in an appropriate amount, and Since the particles are appropriately crosslinked, the compatibility with the resin portion is high, and the rubber particles do not deform even against the shearing force during molding, so that good impact strength and weather resistance can be obtained. That is.

Although it is practically not easy to directly define the graft ratio and the degree of crosslinking of rubber particles, the graft ratio is indirectly defined by the methyl ethyl ketone insoluble gel fraction, and the degree of rubber crosslinking is determined by the swelling index of the gel for toluene. can do.
The gel fraction of the rubber-modified styrenic resin of the present invention (the fraction of the methyl ethyl ketone insoluble portion in the rubber-modified styrenic resin) is 6 to 35% by weight, preferably 6 to 30% by weight, and an index of the degree of crosslinking. The swelling index of the resulting toluene (toluene-insoluble gel component in the rubber-modified styrene resin is fractionated, and the swelling index of the gel component in toluene) is from 8 to 16. Preferably, it is in the range of 9-13.
If the gel fraction is less than 6% by weight, excellent impact resistance cannot be obtained, and if it exceeds 35% by weight, rigidity and workability are reduced. When the swelling index is less than 9, the degree of crosslinking of the rubber particles is excessive and the impact resistance is inferior. On the other hand, when it exceeds 16, the degree of crosslinking of the rubber particles is insufficient and the impact resistance and surface gloss are reduced. .

  1 shows a method for producing the rubber-modified styrenic resin of the present invention. The rubber-modified styrenic resin of the present invention is produced by bulk polymerization or solution polymerization under stirring using a radical initiator, and among them, continuous bulk polymerization or continuous solution polymerization is preferred in terms of productivity and economy. preferable. That is, the partially hydrogenated rubber is dissolved in a raw material solution comprising a styrene monomer / (meth) acrylate monomer and, if necessary, a polymerization solvent, a chain transfer agent, a stabilizer, and additives such as mineral oil. Usually, an organic peroxide is finally added as a radical initiator, but the order of dissolution may be any. The organic peroxide may be added as a raw material solution or a part or all of the organic peroxide may be added to the polymerization solution during the polymerization.

Examples of the organic peroxide used as the radical initiator include peroxy ketals, dialkyl peroxides, diacyl peroxides, peroxy dicarbonates, peroxy esters, ketone peroxides, hydroperoxides, and the like. No. Specifically, examples of the organic peroxide having a half-life of 10 hours of 75 to 100 ° C. include 1.1-bis (t-butylperoxy) cyclohexane and 1.1-bis (t-butylperoxy) 3. 3.5-trimethylcyclohexane, t-butylperoxyisopropyl carbonate, and the like. Examples of the organic peroxide having a 10-hour half-life of 110 to 130 ° C include dicumyl peroxide, t-butylcumyl peroxide, and di-methylperoxide. t-butyl peroxide and the like, and one or more of these are used. Preferably, an organic peroxide having a 10-hour half-life of 75 to 100 ° C. and an organic peroxide having a 10-hour half-life of 110 to 130 ° C. are preferably used in combination. The adjusted raw material solution is supplied to a reactor equipped with a stirrer to perform polymerization. The polymerization temperature is set using a known technique in consideration of the decomposition temperature of the organic peroxide used as the radical initiator, the productivity, the heat removal capability of the reactor, the fluidity of the target rubber-modified styrene resin, and the like. You can do it. The diameter of the rubber particles forming the dispersed phase can be adjusted by a known technique, for example, by controlling the rotation speed of a stirrer. The content of the partially hydrogenated rubber can be achieved by adjusting the content and the polymerization rate of the rubber-like elastic material in the raw material so that the target content is achieved, Can also be achieved by preparing a rubber-modified styrene-based resin containing the same and mixing it with a separately prepared styrene-based resin containing no rubber-like elastic material. However, it is natural that the resin after mixing satisfies all the constituent requirements of the present invention.

Ethylbenzene, toluene, xylene and the like can be used as the polymerization solvent. The polymerization solution exiting the polymerization reactor is led to a recovery device, and the solvent and unreacted monomers are removed by heating and devolatilization. As the recovery device, a device commonly used in the production of a styrene-based resin, for example, a flash tank system, an extruder with a multistage vent, or the like can be used. The devolatilization temperature is in the range of 200 to 300C, preferably 220 to 270C. When the temperature is lower than 200 ° C., the crosslinking of the rubber particles becomes insufficient. On the other hand, when the temperature exceeds 300 ° C., the polymer is decomposed and colored, which is not preferable.
In the method for producing a rubber-modified styrene-based resin of the present invention, as a polymerization apparatus, any of a complete mixing type, a plug flow type, a plug flow type equipped with a circulation device and the like can be suitably used. It is necessary to use at least two or more polymerization devices connected in series.

Further, in the present invention, at any stage before and after the recovery step in the production of the rubber-modified styrene-based resin, or at the extrusion processing stage of the rubber-modified styrene-based resin, at the molding processing stage, various additives commonly used for styrene-based resins, for example, , Inorganic fillers, antistatic agents, heat stabilizers, antioxidants such as hindered phenol-based, phosphorus-based, sulfur-based, light stabilizers, ultraviolet absorbers, processing aids, dispersants, antibacterial agents, nucleating agents, Plasticizers, lubricants, flame retardants, dyes, pigments, colorants and the like can be added.
Here, examples of the inorganic filler include talc, mica, kaolin, calcium carbonate, barium sulfate, clay, glass flake, and glass fiber. Preferably, talc and calcium carbonate are used.

Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber. Examples of the benzotriazole-based ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, and 2- (3 , 5-Di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy- 5'-t-octylphenyl) benzotriazole. Preferably, it is 2- (5-methyl-2-hydroxyphenyl) benzotriazole.
The light stabilizer includes, for example, a hindered amine light stabilizer. Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) separate, N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis [ N-butyl-N- (1,2,2,6,6-pentamethyl-4piperidyl) amino] -6-chloro-1,3,5-triazine condensate. Preferably, bis (2,2,6,6-tetramethyl-4-piperidyl) separate is used.

The added amount of the ultraviolet absorber and the light stabilizer is preferably 0.2 to 2.0 parts by weight based on 100 parts by weight of the rubber-modified styrene resin in the total amount of the ultraviolet absorber and the light stabilizer. More preferably, it is 0.4 to 1.5 parts by weight.
The impact strength can be further increased by adding polydimethylsiloxane, mineral oil, metal salts of higher fatty acids, or amides of higher fatty acids.
Further, by adding a terpene-based resin or a terpene-based hydrogenated resin, moldability, heat resistance, impact resistance, rigidity balance and appearance characteristics can be improved.
The laminate of the present invention comprises, as a base material, a layer made of a styrene resin or vinyl chloride resin (II) other than (I), and a part or the whole of the base material is made of a rubber-modified styrene resin (I). It is a laminate characterized by being coated with a layer. Examples of the styrene resin other than (I) include polystyrene, impact-resistant polystyrene, AS resin, ABS resin, MS resin, transparent HIPS resin, transparent ABS resin, and styrene- (meth) acrylate-butadiene rubber copolymer. A coalesced resin, a styrene- (meth) acrylic acid copolymer resin, a styrene-maleic anhydride copolymer resin and the like can be mentioned, and these can be used alone or in combination.

In the layer composed of (II) in the laminate of the present invention, like the rubber-modified styrene resin (I), an inorganic filler, an antistatic agent, a heat stabilizer, a hindered phenol type, a phosphorus type, a sulfur type. Antioxidants, light stabilizers, ultraviolet absorbers, processing aids, dispersants, antibacterial agents, nucleating agents, plasticizers, lubricants, flame retardants, dyes, pigments, coloring agents, and the like.
For the layer composed of (II) in the laminate of the present invention, wood powder-blended resin other than (I), such as styrene resin or vinyl chloride resin, can be used. The wood flour used here is not particularly limited to the type of tree, but is used, for example, in trees such as hinoki, fir pine, larch, cedar, toga, beech, maple, fir, cherry, bamboo, and houses, and the like. Examples include crushed waste materials and sawdust from sawmills. Also included are crushed products such as rice husks, fruit husks, corn cobs, paper, and pulp. Usually, those having a mesh pass of 60 mesh or less are preferably used.
In the layer of (II) in the laminate of the present invention, a foam of a styrene resin or a vinyl chloride resin other than (I) can be used. About a foaming agent and a foaming method, it can implement by a well-known method. As the foaming agent, a physical foaming agent or a chemical foaming agent can be used. For example, as the physical foaming agent, an inorganic system such as air, carbon dioxide, and nitrogen gas, and an organic system such as butane, pentane, and hexane can be used. As the chemical foaming agent, inorganic systems such as bicarbonate, carbonate, sodium carbonate + acid, azo compounds, hydrazine derivatives, nitroso compounds and the like can be used.

For the layer composed of (II) in the laminate of the present invention, recycled polystyrene, impact-resistant polystyrene, ABS resin, vinyl chloride-based resin, and resin mixed with wood powder thereof can be used. The shape of the recycled material needs to be cut and pulverized from the viewpoint of securing stability during processing. Preferably, it is a recycled resin pellet obtained by processing a recycled material with a kneading machine.
The rubber-modified styrenic resin of the present invention can be molded by injection molding, press molding, sheet extrusion molding, profile extrusion molding, vacuum molding, blow molding, foam molding, or the like. The laminate of the present invention can be formed by multi-layer coextrusion molding, two-color injection molding, insert molding, multilayer hollow molding, multilayer profile extrusion molding, or the like.

According to the present invention, a layer made of a styrene-based resin or vinyl chloride-based resin (II) other than (I) serving as a base material layer and a layer made of a rubber-modified styrene-based resin (I) serving as a coating layer are heat-sealed. Alone can provide a sufficient interfacial adhesive strength. That is, in the present invention, when a laminate is obtained, a commonly used adhesive is not required. This is also a major feature of the present invention.
In addition, the rubber-modified styrene-based resin and laminate of the present invention have excellent weather resistance and impact resistance, and are used in the fields of automobiles, home appliances and miscellaneous goods, and housing and building materials including exterior products such as exteriors. Can be used widely. Particularly, it is suitably used for rain gutters, gables, body gaps, air conditioner duct covers, bamboo fences, fences, lattices, planters, and the like, which are outdoor products of housing equipment and building materials.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited at all by these examples.
The following method was used for the measurement of the partially hydrogenated rubber.
(1) 5% by weight styrene solution viscosity: measured using a 5% by weight solution of styrene as a solvent at 25 ° C. using a Cannon-Fenske viscometer. The unit is cps.
(2) Hydrogenation ratio and microstructure (unsaturated 1,2-vinyl bond): analyzed by FT-NMR. (The details of the measurement followed the procedure described in JP-A-64-90208.)

The following method was used for the measurement of the rubber-modified styrene resin and the laminate.
(1) Dispersed particle diameter: An ultra-thin section having a thickness of 70 nm was prepared from a rubber-modified styrene-based resin dyed with osmium tetroxide, photographed with an electron microscope, and photographed at a magnification of 10,000 times. The particle diameter of 500 to 1000 dispersed particles in the photograph was measured, the weight average particle diameter was calculated by the following equation, and the value was defined as the dispersed particle diameter.
Dispersed particle size = ΣniDi ⁴ / ΣniDi ³
Here, ni is the number of particles of the rubber-like elastic material having the particle diameter Di, and the particle diameter Di is the particle diameter when the circle area is determined from the particle area in the photograph. This measurement was performed using an image analyzer IP-1000PC (manufactured by Asahi Kasei Corporation).
(2) Rubber-like elastic material content: A solution before removing the solvent and unreacted monomer from the rubber-modified styrene resin immediately after polymerization is collected. It is dried under a reduced pressure of 230 ° C.-10 mmHg, and the weight% of the solid content in the polymerization solution is determined. From this value and the weight% of the rubber-like elastic material contained in the raw material solution before polymerization, the weight% of the rubber-like elastic material contained in the rubber-modified styrene resin was determined.

(3) Resin phase Styrene resin composition: A rubber-modified styrene resin is dissolved in methyl ethyl ketone containing 10% by volume of methanol and centrifuged at 20,000 rpm with a centrifuge (Himac CR-20 manufactured by Hitachi, Ltd. (rotor: R20A2)). After the treatment for 60 minutes, the precipitate and the supernatant are separated, and the supernatant is added to a large amount of methanol to precipitate the styrene resin portion in the rubber-modified styrene resin. The precipitate is taken out and dried under reduced pressure of 50 ° C. and 100 mmHg. ¹ H is measured on the dried sample under the following conditions using JASCO Corporation JNM-G400 FT-NMR.
Pulse width = 8.4 μs, data point = 16384, repetition time = 7.559 seconds, integration frequency = 1000, sample concentration = 10 wt%, solvent = 1,1,2,2-tetrachloroethane (d ₂ ), sample Tube = 5 mmφ, measurement temperature = 120 ° C. The peak derived from the phenyl group of the styrene-based monomer is 6.2 to 7.4 ppm, and the peak derived from hydrogen of the acrylate-based monomer is 3.4 to 3. Appears at 8 ppm. Further, a peak derived from hydrogen of the methyl group of the methacrylate monomer appears at 0.2 to 1.1 ppm. The peak area ratio was determined by performing a peak separation operation, and the composition weight ratio of the styrene resin portion was determined from this value. From this value and the rubber-like elastic body content obtained in the above (2), the weight% of each monomer component in the rubber-modified styrenic resin was obtained.

(4) Charpy impact strength: measured according to ISO 179.
(5) Methyl ethyl ketone insoluble gel fraction: 1 g of rubber-modified styrene resin is precisely weighed (W1), 20 ml of methyl ethyl ketone is added, shaken at 23 ° C. for 2 hours, and then centrifuged (Himac CR manufactured by Hitachi, Ltd.). -20 (rotor: R20A2)) and centrifuged at 20,000 rpm for 60 minutes at 10 ° C or lower. The supernatant is decanted off to obtain insolubles. Subsequently, vacuum drying is performed for 1 hour at 160 ° C. and 20 mmHg or less, and after cooling to room temperature in a desiccator, the weight of the insoluble matter is precisely weighed (W2). The methyl ethyl ketone insoluble matter gel fraction is determined by the following formula.
Methyl ethyl ketone insoluble gel fraction (%) = (W2 / W1) × 100
(6) Swelling index with respect to toluene: 1 g of a rubber-modified styrene resin was precisely weighed (W3), 20 ml of toluene was added, and the mixture was shaken at 23 ° C. for 2 hours, and then centrifuged (Himac CR-20 manufactured by Hitachi, Ltd.). (Rotor: R20A2)) at 10 ° C. or lower at 20,000 rpm for 60 minutes. The supernatant is removed by decantation, and the weight of the insoluble matter containing toluene is precisely weighed (W4). Subsequently, vacuum drying is performed for 1 hour at 160 ° C. and 20 mmHg or less, and after cooling to room temperature in a desiccator, the weight of the insoluble matter is precisely weighed (W5). The swelling index for toluene is determined by the following equation.
Swelling index for toluene = (W4 / W5)

(7) Weather resistance Color difference:
(Preparation of weather resistance test sample)
The mixture was mixed according to the following formulation, and the colorant and the weathering agent were melt-kneaded with an extruder to obtain white colored pellets.
Rubber-modified styrene resin 100 parts by weight Pigment Titanium oxide 2.4 parts by weight Lubricant Ethylene bis stearamide 0.6 parts by weight Weathering agent 2- (5-methyl-2-hydroxyphenyl) benzotriazole (Ciba Specialty Chemicals) (Tinuvin P)
0.4 parts by weight of a weathering agent bis (2,2,6,6-tetramethyl-4-piperidyl) separate (Sankyo LS-770) 0.8 part by weight A 50 × 2 mm flat plate was formed and cut out to obtain a sample for evaluating weather resistance. The weather resistance was evaluated under the following conditions.

(Weather resistance evaluation conditions)
The obtained sample for weather resistance evaluation was exposed to a metal weather [Model: KU-R5C1-A manufactured by Daipla Wintes Co., Ltd.] using a metal halide lamp (using a KF-1 filter) as a light source for 800 hours, and measured with a color difference meter. The color difference (ΔE *) was measured. The color difference measurement was performed every 200, 400, 600, and 800 hours of the exposure time, and the maximum value of the measured values was defined as the value of weather resistance color difference (ΔE *).
Metal weather test conditions:
Energy intensity of light source 75mW / cm ²
Operation mode (lamp irradiation) Black panel temperature 63 ℃, humidity 50RH%
(Condensation) Black panel temperature 30 ° C, humidity 98RH%
(Water spray) 30 seconds before and after condensation
The test was performed with a cycle of 4 hours each for lamp irradiation and dew condensation.
Color difference measurement conditions C light 2 ° field of view

(9) Evaluation of Laminate Adhesion After conditioning each of the laminates at 23 ° C. for 24 hours, the laminate was formed of (II) by penetrating the layer of (I) according to JIS K5400 adhesive grid tape method. A cut was made with a cut of 5 mm between the cuts reaching the layer, and the measurement was performed.
Less than 30% defect rate: ○ More than 30% defect rate: ×
<Example of rubber-modified styrene resin production>
[Production of conjugated diene rubber and partially hydrogenated rubbers A0 to A4]
A butadiene / n-hexane mixed solution (butadiene concentration 20% by weight, containing 100 ppm of tetramethylethylenediamine) at a rate of 20 liter / hr was added to n-butyl using a 10 liter inner volume autoclave equipped with a stirrer and jacket as a reactor. A lithium / n-hexane solution (concentration: 5% by weight) was introduced at 70 ml / hr, and continuous polymerization of butadiene was carried out at a polymerization temperature of 110 ° C. The obtained active polymer was deactivated with methanol, 8 liter of the polymer solution was transferred to another reactor having a 10-liter internal volume equipped with a stirrer and jacket, and heated at 60 ° C. as di-p-hydrogenation catalyst. 250 ml of a tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration: 1 mmol / l) and 50 ml of an n-butyllithium solution (concentration: 5 mmol / l) were added at 0 ° C. and 2.0 kg / cm ² . The mixture mixed under a hydrogen pressure was added and reacted at a hydrogen partial pressure of 3.0 Kg / cm ^{2 for} 30 minutes. A stabilizer was added to the obtained partially hydrogenated polymer solution, and the solvent was removed. Table 1 shows the analysis values of the rubber-like elastic material of the polymer A0 before partial hydrogenation and the partially hydrogenated polymer A1 obtained by sampling after methanol deactivation and adding a stabilizer and removing the solvent. The butadiene polymer obtained in the same manner as the polymer A0 was hydrogenated under the same conditions as the partially hydrogenated polymer A1 except that the hydrogenation reaction time was changed, and the partially hydrogenated polymers A2 having different hydrogenation rates were obtained. A4 was obtained. The analytical values of these rubber-like elastic materials are also shown in Table 1.

(Examples 1 to 4)
Dissolve 9.6 parts by weight of rubber-like elastic body A2 in 39.2 parts by weight of styrene, 39.2 parts by weight of methyl methacrylate, and 12.0 parts by weight of ethylbenzene, and then dissolve in 1,1 bis (t-butylperoxy) cyclohexane 0 0.02 parts by weight and 0.4 parts by weight of α-methylstyrene dimer as a chain transfer agent were added to prepare a raw material solution. The raw material solution was continuously supplied at a rate of 3.0 L / hr to a polymerization apparatus in which three tower reactors each having a stirrer (each having an inner volume of 6.2 L) were connected in series. The polymerization was carried out at a polymerization temperature of 128 ° C. in the first reactor, 135 ° C. in the second reactor, and 155 ° C. in the third reactor. The obtained polymerization solution was continuously supplied to a devolatilizing extruder equipped with a two-stage vent, and an unreacted monomer and a solvent were recovered to obtain a rubber-modified styrene resin. The devolatilizing extruder had a temperature of 200 to 260 ° C. and a degree of vacuum of 20 torr. The dispersed particle diameter was adjusted by the number of stirring by a stirrer, the amount of 1,1 bis (t-butylperoxy) cyclohexane, and the amount of α-methylstyrene dimer. Further, the polymerization temperature was adjusted as needed. The analysis and evaluation results are shown in Table 2.

(Example 5)
The same operation as in Examples 1 to 4 was performed except that 6.4 parts by weight of the rubber-like elastic body A2, 40.8 parts by weight of styrene, 40.8 parts by weight of methyl methacrylate, and 0.3 part by weight of α-methylstyrene dimer were used. Thus, a rubber-modified styrenic resin was obtained. The analysis and evaluation results are shown in Table 2.
(Example 6)
A rubber-modified styrene resin was obtained in the same manner as in Examples 1 to 4, except that 63.5 parts by weight of styrene, 14.9 parts by weight of methyl methacrylate, and 0.3 part by weight of α-methylstyrene dimer were used. The analysis and evaluation results are shown in Table 2.
(Example 7)
Except having set it as the rubber-like elastic body A1, it carried out similarly to Example 1-4, and obtained the rubber modified styrene resin. The analysis and evaluation results are shown in Table 2.
(Example 8)
A rubber-modified styrene resin was obtained in the same manner as in Examples 1 to 4, except that the rubber-like elastic body A3 was used. The analysis and evaluation results are shown in Table 2.
(Example 9)
A rubber-modified styrene resin was obtained in the same manner as in Examples 1 to 4, except that 39.2 parts by weight of styrene, 34.5 parts by weight of methyl methacrylate, and 4.7 parts by weight of butyl acrylate were used. The analysis and evaluation results are shown in Table 2.
(Example 10)
Two kinds of weathering agents were not added to the rubber-modified styrene resin obtained in Example 1 at the time of preparing a sample for evaluating weathering resistance. Table 2 shows the evaluation results.

(Comparative Example 1)
Rubber-like elastic material A0 4.8 parts by weight, styrene 83.2 parts by weight, 1,1 bis (t-butylperoxy) cyclohexane 0.01 parts by weight, α-methylstyrene dimer 0.1 parts by weight By operating in the same manner as in Examples 1 to 4, a rubber-modified styrenic resin was obtained. Table 3 shows the analysis and evaluation results.
(Comparative Example 2)
Except that 9.6 parts by weight of rubber-like elastic body A2, 78.4 parts by weight of styrene, and 0.3 part by weight of α-methylstyrene dimer were used, the same operation as in Examples 1 to 4 was carried out to obtain a rubber-modified styrene resin. Was. Table 3 shows the analysis and evaluation results.
(Comparative Example 3)
A matrix resin having the same monomer composition as in Example 1 was mixed and kneaded with the rubber-modified styrenic resin obtained in Example 1 by an extruder to make the final rubber-like elastic body amount 2% by weight. Table 3 shows the evaluation results.
(Comparative Example 4)
A rubber-modified styrene resin was obtained in the same manner as in Examples 1 to 4, except that the rubber-like elastic body A0 was used. Table 3 shows the analysis and evaluation results.
(Comparative Example 5)
A rubber-modified styrene resin was obtained in the same manner as in Examples 1 to 4, except that the rubber-like elastic body A4 was used. Table 3 shows the analysis and evaluation results.

(Comparative Example 6)
A rubber-modified styrenic resin was obtained in the same manner as in Example 1, except that 6.4 parts by weight of the rubber-like elastic body A2, 13.9 parts by weight of styrene, and 67.7 parts by weight of methyl methacrylate were used. Table 3 shows the analysis and evaluation results.
(Comparative Example 7)
The rubber-modified styrenic resin obtained in Comparative Example 1 was not added with two kinds of weathering agents at the time of preparing a sample for evaluating weathering resistance. Table 3 shows the evaluation results.

〈積層体実施例〉
積層体に用いた樹脂は以下の通りである。
（Ｉ）
ゴム変性スチレン系樹脂Ｈ２、Ｈ６、Ｈ９、Ｈ１１、Ｈ１６を用いた。
（ＩＩ）
Ｂ１：耐衝撃性ポリスチレン ＰＳジャパン（株）製 ＰＳＪポリスチレン ４７５Ｄ
Ｂ２：ＡＢＳ樹脂 旭化成ケミカルズ（株）製 スタイラックＡＢＳ １２０Ｂ
Ｂ３：塩化ビニル樹脂

<Laminate Example>
The resins used for the laminate are as follows.
(I)
Rubber-modified styrene resins H2, H6, H9, H11 and H16 were used.
(II)
B1: Impact-resistant polystyrene PSJ polystyrene 475D manufactured by PS Japan Co., Ltd.
B2: ABS resin Stylac ABS 120B manufactured by Asahi Kasei Chemicals Corporation
B3: Vinyl chloride resin

(Examples 11 to 15, Comparative Examples 8 to 12)
As a weather resistance test sample, a 180 × 150 × 0.2 mm sheet is prepared by compression-molding each of the white-colored resins (I) to which a coloring agent and a weathering agent are added. Each resin of (II) is compression molded to form a sheet of 180 × 150 × 3 mm. Then, each of the sheets (I) and (II) was inserted into a mold of 180 × 150 × 3 mm, preheated at 200 ° C. for 5 minutes, and then 2MP.
The sheet was pressed under the pressure of a for 1 minute, and further cooled by a water-cooled cooling press to obtain a laminate. The laminate was cut out to prepare a sample for evaluating weather resistance. The layer composed of (I) was used as an exposed surface, and the weather resistance was evaluated. Moreover, the adhesiveness of the obtained laminate was evaluated. Table 4 shows the evaluation results.

The rubber-modified styrenic resin obtained by the production method of the present invention is a material having excellent weather resistance, impact resistance, and excellent moldability and colorability. The rubber-modified styrenic resin of the present invention and a laminate using the resin can be used in a wide range of applications such as the field of automobiles, home appliances and miscellaneous goods, and the field of housing and building materials including outdoor products such as exteriors. Particularly, it can be suitably used as an outdoor product and a building material in the field of housing and building materials.

Claims (14)

  Partially hydrogenated rubber (A) in which 7 to 70 mol% of the unsaturated units of the conjugated diene rubber is hydrogenated, styrene monomer (B), and (meth) acrylate monomer (C) And (A) + (B) + (C) as 100 parts by weight, (A) is 3 to 16 parts by weight, and the weight ratio of (B) / (C) is 20/80 to 82/18. In the above, bulk polymerization or solution polymerization is carried out with stirring using a radical initiator, and the obtained rubber-modified styrene resin has a methyl ethyl ketone insoluble content gel fraction of 6 to 35% by weight, and a swelling index of the gel for toluene. The method for producing a rubber-modified styrenic resin, characterized in that the polymerization is carried out so as to be 8 to 16.   2. The process according to claim 1, wherein the partially hydrogenated rubber (A) has a 5% by weight styrene solution viscosity at 25 [deg.] C. of 20 to 150 centipoise.   3. The method according to claim 1, wherein in the partially hydrogenated rubber (A), the conjugated diene rubber before hydrogenation is polybutadiene.   Partially hydrogenated rubber (A) in which 7 to 70 mol% of the unsaturated units of the conjugated diene rubber is hydrogenated, styrene monomer (B), and (meth) acrylate monomer (C) And (B) / (C) in a weight ratio of 20/80 to 82/18 by a bulk polymerization or a solution polymerization under stirring with a radical initiator to obtain a dispersed rubber particle phase. And a rubber-modified styrene resin composed of a resin phase and a copolymer constituting the resin phase, wherein the styrene monomer unit and the (meth) acrylate monomer unit are 20/80 to 80 / A rubber having a rubber-modified styrene resin having a methyl ethyl ketone-insoluble content gel fraction of 6 to 35% by weight and a swelling index of the gel in toluene of 8 to 16; Denatured steel Emissions-based resin.   The rubber-modified styrene resin according to claim 4, wherein in the partially hydrogenated rubber (A), the conjugated diene rubber before hydrogenation is polybutadiene.   The rubber-modified styrenic resin according to claim 4, wherein the rubber particle diameter of the dispersed rubber particle phase is 0.5 to 3.5 μm.   7. The rubber modification according to claim 4, wherein the styrene monomer (B) is styrene, and the (meth) acrylate monomer (C) is methyl methacrylate or methyl methacrylate and butyl acrylate. Styrene resin.   Partially hydrogenated rubber (A) in which 7 to 70 mol% of the unsaturated units of the conjugated diene rubber is hydrogenated, styrene monomer (B), and (meth) acrylate monomer (C) And (B) / (C) in a weight ratio of 20/80 to 82/18 by a bulk polymerization or a solution polymerization under stirring with a radical initiator to obtain a dispersed rubber particle phase. And a rubber-modified styrenic resin comprising a resin phase, wherein the styrene-based monomer unit and the (meth) acrylate-based monomer unit are 20/80 to 80 / A rubber-modified styrene resin having a weight ratio of 20 to 20%, a gel fraction of methyl ethyl ketone insoluble in the obtained rubber-modified styrene resin of 6 to 35% by weight, and a swelling index of the gel for toluene of 8 to 16 ( I) Laminate and a layer comprising an Ranaru layer (I) other than the styrene-based resin or vinyl chloride resin (II) is characterized by having a laminated structure.   9. The laminate according to claim 8, wherein the rubber particle diameter of the dispersed rubber particle phase is 0.5 to 3.5 [mu] m.   The laminate according to any one of claims 8 to 9, wherein the layer comprising (I) and (II) is heat-sealed.   10. The laminate according to claim 8, wherein in the layer comprising (II), the styrene resin other than (I) is at least one selected from polystyrene, impact-resistant polystyrene, and ABS resin.   The laminate according to any one of claims 8 to 9, wherein the layer composed of (II) is a styrene-based resin or a vinyl chloride-based resin other than (I) containing wood powder.   The laminate according to claim 8, wherein the layer comprising (II) is a foam of a styrene resin or a vinyl chloride resin other than (I).   The laminate according to any one of claims 8 to 9, wherein the layer comprising (II) is recycled polystyrene, impact-resistant polystyrene, ABS resin, vinyl chloride-based resin, and a resin containing wood powder thereof.