JP2009113471A - Layered product and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a layered product which comprises a foamed layer made of foam, that has an expansion ratio as high as 2 or above, is lightweight and is clearly colored in an even tint, spotty-pattern tints, etc., and a transparent resin layer disposed on at least one side of the foamed layer, which is free from distortion and has excellent smoothness and in which a spotty-pattern that the foamed layer bears is clearly recognized through the resin layer and hence which has an excellent appearance and to provide a process for producing the layered product. <P>SOLUTION: The layered product comprises a first layer (foamed layer) 11 and a second layer (resin layer) 12. The first layer (foamed layer) 11 is made of the foam which is formed from a composition comprising a thermoplastic resin containing 5 to 100 mass% of a styrene resin, a colorant and a foaming agent containing a compound of -10 to 55°C boiling point and in which content of the colorant is 0.01 to 15 parts mass and content of the foaming agent is 0.1 to 5 parts mass respectively toward 100 parts mass of the thermoplastic resin. The second layer (resin layer) 12 is disposed on at least one side of the first layer 11, has total light transmittance of 50% or more when a test piece of 2.5 mm thickness is measured in accordance with ASTM D1003 and is made of a thermoplastic resin composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminate comprising a layer made of a colored and / or patterned resin foam and a transparent resin layer disposed on at least one side of the layer, and a method for producing the same.

Styrenic resins such as ABS resins are widely used because of their excellent mechanical properties, physical properties, moldability, and the like. For example, in building material applications, a method of extruding resin pellets pre-colored in several different colors, for example, brown, etc. without completely mixing inside the mold in order to obtain a molded product having a wood texture, etc. Is adopted (see, for example, Patent Documents 1 to 3). Moreover, the laminated body which consists of a transparent layer, a woodgrain layer, and a base material is also known (for example, refer patent document 4 grade | etc.,).
However, in recent years, there has been a demand for a material that gives a molded article for building materials that is excellent in weight reduction, durability, and the like. For example, a material made of a resin composition containing a resin and a foaming agent has been studied.

Japanese Patent Laid-Open No. 10-60202 JP 11-43582 A JP-A-11-310683 JP 2004-74746 A

  The object of the present invention is to provide a foam layer having a foaming ratio of 2 times or more and light weight, and a foam layer composed of a foam that is more vividly colored than conventional ones, and at least of this layer. It has a transparent resin layer (protective layer) arranged on one side, has no distortion, is excellent in smoothness, and the pattern that appears on the foamed layer is clearly recognized through the resin layer, improving the appearance. The object is to provide an excellent laminate and a method for producing the same.

The present invention is shown below.
1. (A) When the whole is 100% by mass, a thermoplastic resin containing 5 to 100% by mass of a styrene resin, (B) a colorant, and (C) a compound having a boiling point of −10 ° C. to 55 ° C. The content of the colorant (B) and the foaming agent (C) is 0.01 to 15 parts by weight and 0 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), respectively. A first layer made of a foam of 1 to 5 parts by mass, and a total light transmission according to ASTM D1003 with respect to a test piece of 2.5 mm thickness disposed on at least one side of the first layer And a second layer made of a thermoplastic resin composition [Y] having a rate of 50% or more.
2. 2. The laminate according to 1 above, wherein the surface of the first layer has a spotted pattern.
3. 3. The thermoplastic resin composition [Y] according to 1 or 2 above, wherein the thermoplastic resin composition [Y] contains at least one selected from a rubber-reinforced resin, a polycarbonate resin, a polyester resin, a thermoplastic elastomer, an acrylic resin, and a vinyl chloride resin. Laminated body.
4). The laminate according to any one of 1 to 3 above, wherein the density of the first layer is 40 to 500 kg / m ³ .
5). The laminated body in any one of said 1 thru | or 4 which is a film or a sheet | seat.
6). The laminate according to any one of 1 to 5 above, which is used as a substitute for a wooden product.
7). It is a manufacturing method of the laminated body in any one of said 1 thru | or 6, Comprising: The thermoplastic resin corresponded to 5-50 mass% of the said thermoplastic resin (A), and 0-50 of the said coloring agent (B). Composition [X1] containing a coloring agent corresponding to mass% and a foaming agent corresponding to 20 to 100 mass% of the foaming agent (C), and 50 to 95 mass of the thermoplastic resin (A). % Of a thermoplastic resin, a colorant corresponding to 50 to 100% by mass of the colorant (B), and a foaming agent corresponding to 0 to 80% by mass of the foaming agent (C). A thermoplastic resin composition [X] containing the product [X2] and a thermoplastic resin composition [Y] having a total light transmittance of 50% or more according to ASTM D1003 with respect to a test piece having a thickness of 2.5 mm; A process for producing a laminate comprising the step of co-extrusion.
8). The manufacturing method of the laminated body of said 7 whose said composition [X1] is a foaming agent containing masterbatch with an expansion ratio of 1.15 or less.
9. When the acetone-soluble component obtained by immersing the styrenic resin contained in the composition [X1] in acetone is 100% by mass as a whole, a monomer unit composed of an aromatic vinyl compound ( Monomer unit derived from aromatic vinyl compound) 75 to 95% by mass, monomer unit composed of vinyl cyanide compound (monomer unit derived from vinyl cyanide compound) 5 to 25% by mass, and others The manufacturing method of the laminated body of said 7 or 8 comprised by the monomer unit (monomer unit derived from another compound) 0-20 mass% which consists of said compound.

According to the present invention, the first layer (foaming layer) made of a foam that has a foaming ratio as high as 2 times or more, is light, and is colored and / or provided with a mottled pattern, wood grain pattern, and the like, A transparent second layer (protective layer) disposed on at least one side of the layer, having no distortion, excellent smoothness, and the pattern appearing on the first layer (foamed layer) is the second layer It is possible to provide a laminate that is clearly recognized through a layer (protective layer) and excellent in appearance and a method for producing the same.
In the laminate of the present invention, since the foam cells of the first layer are uniform, the shape stability is excellent, uniform color coloring and spotted pattern coloring can be vividly colored, and in particular, the spotted pattern coloring is more vividly colored. Can do. In addition, since the second layer is transparent or translucent, the texture imparted by the surface of the foam of the first layer can be visually recognized through the second layer, and as an alternative to a wooden product, For example, civil engineering / construction-related materials such as display boards; interior / exterior materials for vehicles; electrical / electronic parts; sports equipment; walls, floors, frames, furniture (desk drawers, top plates, etc.), decorative sheets, partitions, lattices , Fences, gutters, sizing boards, carports, terraces, decks, bathroom components (counters, doors, apron, UB frames, window frames, shelves, etc.), kitchen components (doors, dividers, window frames, shelves, etc.), etc. It can be preferably used for interior / exterior materials for houses and offices.
According to the method for producing a laminate of the present invention, a laminate that is lightweight, has a clear coloration such as uniform color coloring and spotted pattern coloring by a colorant, has no distortion, and has excellent smoothness and shape stability. Can get well.
When the composition [X1] is a foaming agent-containing masterbatch having an expansion ratio of 1.15 or less, the expansion ratio is as high as 2 times or more, it is lightweight, and is preferably colored. And a resin layer disposed on at least one side of the layer, the uniform color coloring by the coloring agent, the mottled pattern coloring, etc. are clear, no distortion, and smoothness It is suitable for forming a laminate having excellent appearance and shape stability.

  The present invention will be described in detail below. In the present invention, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acrylic and methacrylic.

1. Laminate The laminate of the present invention is a thermoplastic resin containing 5 to 100% by mass of a styrene resin (hereinafter also referred to as “component (A)”), when (A) is 100% by mass. B) a colorant (hereinafter also referred to as “component (B)”) and (C) a foaming agent having a boiling point of −10 ° C. to 55 ° C. (hereinafter also referred to as “component (C)”). The content of the colorant (B) and the foaming agent (C) is 0.01 to 15 parts by mass and 0.1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A), respectively. A test piece having a thickness of 2.5 mm and a first layer (hereinafter also referred to as a “foamed layer”) made of a foam as a part, and disposed on at least one side of the first layer (foamed layer). On the other hand, the second layer (hereinafter referred to as the thermoplastic resin composition [Y] having a total light transmittance of 50% or more according to ASTM D1003). Also referred to as "protective layer".) And characterized in that it comprises a.

1-1. First layer (foamed layer)
This foam layer is a layer made of a foam containing components (A), (B) and (C) in a predetermined ratio. That is, this foam layer is a layer in which uniform foam cells are contained in the wall material containing the components (A) and (B). Foamed cells usually contain component (C) and are adjacent to each other.

  The said component (A) contains 5-100 mass% of styrene resin (henceforth "styrene resin (A1)") when the whole is 100 mass%. Therefore, the said component (A) consists of 1 or more types of the said styrene resin (A1), or 1 or more types of the said styrene resin (A1), and another thermoplastic resin.

  This styrene resin (A1) is a polymer containing a monomer unit derived from an aromatic vinyl compound. That is, the styrene resin (A1) is a monomer composed of one or more aromatic vinyl compounds, or one or more monomers copolymerizable with one or more aromatic vinyl compounds. A styrene-based (co) polymer obtained by (co) polymerizing monomers (hereinafter, both monomers are collectively referred to as “vinyl monomer (b1)”) ( A11) and / or other monomer capable of copolymerization with one or more monomers of an aromatic vinyl compound or one or more aromatic vinyl compounds in the presence of a rubbery polymer A rubber-reinforced styrene resin (hereinafter referred to as “vinyl monomer (b2)”) obtained by polymerizing monomers comprising at least one kind of body (hereinafter, both monomers are collectively referred to as “vinyl monomer (b2)”). A12). The rubber-reinforced styrene resin (A12) is usually composed of a grafted rubber polymer in which the vinyl monomer (b2) is graft-polymerized to a rubber polymer, and the vinyl polymer that is not grafted. It is a resin containing the (co) polymer of the monomer (b2).

  The aromatic vinyl compound constituting the vinyl monomer (b1) is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. . Examples thereof include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, p-tert-butyl styrene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

The styrenic (co) polymer (A11) as the styrenic resin (A1) may be either a homopolymer or a copolymer, or a combination thereof. A copolymer is preferred.
When the styrenic (co) polymer (A11) is a copolymer, other monomer units other than the monomer unit derived from the aromatic vinyl compound include vinyl cyanide compounds and (meth) acrylic. Monomer units derived from acid ester compounds, maleimide compounds, acid anhydrides, and vinyl compounds having functional groups such as hydroxyl groups, amino groups, epoxy groups, amide groups, carboxyl groups, oxazoline groups, etc. Can be mentioned. These other monomer units may be included singly or in combination of two or more.

  Among the other monomers copolymerizable with the aromatic vinyl compound, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Can be mentioned. These can be used alone or in combination of two or more. In addition, as another method of introducing a unit derived from a maleimide compound, for example, a method of copolymerizing maleic anhydride and then imidizing may be used.
Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.

  Examples of the vinyl compound having a functional group such as hydroxyl group, amino group, epoxy group, amide group, carboxyl group, or oxazoline group include 2-hydroxyethyl (meth) acrylate, hydroxystyrene, and (meth) acrylic. Acid N, N-dimethylaminomethyl, N, N-diethyl-p-aminomethylstyrene, glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, methallyl glycidyl ether, allyl Examples thereof include glycidyl ether, methacrylamide, acrylamide, (meth) acrylic acid, vinyl oxazoline and the like. These can be used alone or in combination of two or more.

  When the styrene-based (co) polymer (A11) is a copolymer, a preferable copolymer is a styrene-based polymer using a vinyl monomer (b1) containing an aromatic vinyl compound and a vinyl cyanide compound. It is a copolymer. More preferably, it is a copolymer comprising a monomer unit derived from an aromatic vinyl compound, a monomer unit derived from a vinyl cyanide compound, and other monomer units contained as necessary. In this case, the content ratio of these monomer units is preferably 50 to 97% by mass, 3 to 50% by mass, and 0 to 47% when the total of all the monomer units is 100% by mass, respectively. It is mass%, More preferably, it is 55-95 mass%, 5-45 mass%, and 0-15 mass%. If it is the said content rate, it can be set as the foaming layer which was excellent in chemical resistance and maintained the high expansion ratio.

  When the styrene-based (co) polymer (A11) is a copolymer, acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, acrylonitrile / styrene -N-phenylmaleimide copolymer etc. are mentioned.

  Regarding the styrene-based (co) polymer (A11), the polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) by gel permeation chromatography (GPC) is preferably 100,000 to 300,000. More preferably, it is 100,000-270,000, More preferably, it is 120,000-250,000. When the Mw is within this range, the content of the foaming agent (C) in the foam layer is stable, and the change in the content over time can be reduced.

  The styrene (co) polymer (A11) is produced by polymerizing a vinyl monomer (b1) containing an aromatic vinyl compound in the presence or absence of a polymerization initiator. be able to. When a polymerization initiator is used as the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and these polymerization methods may be used in combination. Moreover, when not using a polymerization initiator, it can be set as thermal polymerization.

As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b1) whole quantity.
In addition, the chain transfer agent, emulsifier, etc. which can be used at the time of manufacture of the rubber reinforcement | strengthening styrene-type resin (A12) mentioned later as needed can be used.

  In the production of the styrene-based (co) polymer (A11), the polymerization may be started in a state where the total amount of the vinyl-based monomer (b1) is accommodated in the reaction system, or a single amount selected arbitrarily. You may superpose | polymerize by adding a body component separately or continuously. Furthermore, when using the said polymerization initiator, it can add to a reaction system collectively or continuously.

  The rubber-reinforced styrene resin (A12) is a resin obtained by polymerizing the vinyl monomer (b2) in the presence of a rubber polymer (hereinafter referred to as “rubber polymer (a)”). It is.

  The rubbery polymer (a) may be a homopolymer or a copolymer as long as it is rubbery at room temperature, but a diene polymer and a non-diene polymer are preferred. . Furthermore, the rubbery polymer (a) may be a crosslinked polymer or a non-crosslinked polymer. These can be used alone or in combination of two or more.

  Examples of the diene polymer include homopolymers such as polybutadiene and polyisoprene; styrene / butadiene copolymer rubbers; styrene / isoprene copolymer rubbers; natural rubbers and the like. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The said diene polymer can be used individually by 1 type or in combination of 2 or more types.

  Examples of the non-diene polymer include ethylene units and ethylene / α-olefin copolymer rubbers containing units derived from α-olefins having 3 or more carbon atoms; urethane rubbers; acrylic rubbers; silicone rubbers. A silicone-acrylic composite rubber; a polymer obtained by hydrogenating a (co) polymer containing a unit derived from a conjugated diene compound (however, the hydrogenation rate is usually 50% or more). . These copolymers may be block copolymers or random copolymers. The said non-diene polymer can be used individually by 1 type or in combination of 2 or more types.

  The rubbery polymer (a) is preferably a diene polymer and a hydrogenated product thereof, an acrylic rubber, and an ethylene / α-olefin copolymer rubber.

  The shape of the rubbery polymer (a) used for forming the rubber-reinforced styrene resin (A12) is not particularly limited, but when it is particulate, the weight average particle diameter is preferably 100 to 2,000 nm. More preferably, it is 200 to 1,000 nm. When the weight average particle diameter is in the above range, the impact resistance of the laminate of the present invention is excellent. The weight average particle diameter can be measured by an image analysis method using an electron micrograph, a laser diffraction method, a light scattering method, or the like.

  When the rubbery polymer (a) is in the form of particles, as long as the weight average particle diameter is within the above range, for example, JP-A-61-233010, JP-A-59-93701, JP The thing enlarged by the well-known method described in 56-167704 gazette etc. can also be used.

  As a method for producing the rubbery polymer (a), emulsion polymerization is preferable in consideration of adjustment of the average particle diameter and the like. In this case, the average particle size can be adjusted by selecting the production conditions such as the type of emulsifier and the amount used, the type and amount of initiator used, the polymerization time, the polymerization temperature, and the stirring conditions. Further, as another method for adjusting the average particle size (particle size distribution), a method of blending two or more of the rubbery polymers (a) having different particle sizes may be used.

  The vinyl monomer (b2) used for forming the rubber-reinforced styrene resin (A12) may be only an aromatic vinyl compound, and this aromatic vinyl compound, for example, a vinyl cyanide compound, (meta It may be a combination of a copolymerizable compound with an aromatic vinyl compound such as an acrylate compound, a maleimide compound or an acid anhydride.

  As the aromatic vinyl compound, compounds exemplified as the aromatic vinyl compound contained in the vinyl monomer (b1) used for the formation of the styrene (co) polymer (A11) may be used alone or in combination. Two or more kinds can be used in combination. Of these, styrene and α-methylstyrene are preferred.

  As the vinyl cyanide compound, compounds exemplified as the vinyl cyanide compound contained in the vinyl monomer (b1) used for the formation of the styrene-based (co) polymer (A11) may be used alone or in combination. Two or more kinds can be used in combination. Of these, acrylonitrile is preferred.

  The (meth) acrylic acid ester compound, maleimide compound, acid anhydride and the like are also included in the vinyl monomer (b1) used for forming the styrene (co) polymer (A11). A compound can be used individually by 1 type or in combination of 2 or more types.

  The vinyl monomer (b2) is preferably used in combination of one or more aromatic vinyl compounds and one or more compounds copolymerizable with the aromatic vinyl compounds. The mass ratio of the group vinyl compound and the other compounds is usually 45 to 97% by mass and 3 to 55% by mass, preferably 50 to 95% by mass, when the total of these is 100% by mass. It is 5-50 mass%. When the ratio of the aromatic vinyl compound is too small, the shape stability of the foamed layer tends to be inferior, and when too large, the chemical resistance, heat resistance, etc. of the foamed layer may not be sufficient.

The vinyl monomer (b2) is preferably a combination of an aromatic vinyl compound and a vinyl cyanide compound, and an aromatic vinyl compound, a vinyl cyanide compound and other compounds ((meth) acrylic ester compounds Etc.). By using the vinyl cyanide compound, the balance of physical properties such as chemical resistance and heat resistance of the foamed layer is improved.
In the vinyl monomer (b1) and the vinyl monomer (b2), the constituent components and the proportions thereof may be the same or different.

  The rubber-reinforced styrene resin (A12) can be produced by polymerizing the vinyl monomer (b2) in the presence of the rubber polymer (a). As the polymerization method, emulsion polymerization, solution polymerization, bulk polymerization, and bulk-suspension polymerization are preferable.

  In the production of the rubber-reinforced styrene resin (A12), the rubber polymer (a) and the vinyl monomer (b2) are added in the reaction system in the total amount of the rubber polymer (a). In the presence of, the vinyl monomer (b2) may be added all at once to initiate the polymerization, or the polymerization may be carried out in portions or continuously. Further, in the presence or absence of part of the rubber polymer (a), the vinyl monomer (b2) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. At this time, the remainder of the rubbery polymer (a) may be added in a batch, divided or continuously during the reaction.

  When producing 100 parts by mass of the rubber-reinforced styrene resin (A12), the amount of the rubbery polymer (a) used is usually 5 to 80 parts by mass. Moreover, the usage-amount of the said vinylic monomer (b2) is 25-1,900 mass parts normally with respect to 100 mass parts of said rubbery polymers (a).

  When the rubber-reinforced styrene resin (A12) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

As said polymerization initiator, the compound illustrated by description of the manufacturing method of the said styrene-type (co) polymer (A11) can be used individually by 1 type or in combination of 2 or more types. The usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b2) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer (b2).
The chain transfer agent can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (b2) whole quantity.

Emulsion polymerization can be carried out under known conditions according to the type of vinyl monomer (b2), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulating with a coagulant to make the resin component powdery, and then washing and drying. As this coagulant, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid are used.
In the case where two or more rubber-reinforced styrene resins (A12) are contained in the styrene resin (A1), the resin components may be isolated from each latex and then mixed. As such, there is a method of coagulating a latex mixture containing each resin component.

  In the case of producing the rubber-reinforced styrene resin (A12) by solution polymerization, bulk polymerization, and bulk-suspension polymerization, known methods can be applied.

  The graft ratio of the rubber-reinforced styrene resin (A12) is usually 10 to 200% by mass, preferably 15 to 150% by mass. When the graft ratio is less than 10% by mass, the foam layer has excellent surface appearance and impact resistance within the above range.

Here, the graft ratio refers to x grams of the rubbery polymer (a) in 1 gram of the rubber-reinforced styrene resin (A12) and 1 gram of the rubber-reinforced styrene resin (A12) dissolved in acetone. When the insoluble matter at the time is defined as y gram, the value is obtained by the following formula. However, when the rubbery polymer (a) is an acrylic rubber, acetonitrile is used instead of acetone.
Graft ratio (mass%) = {(y−x) / x} × 100

  In addition, the intrinsic viscosity [η] of a component soluble in acetone of the rubber-reinforced styrene resin (A12) (provided that acetonitrile is used when the rubbery polymer (a) is an acrylic rubber). (Measured in methyl ethyl ketone at 30 ° C.) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.9 dl / g. When the intrinsic viscosity [η] is within the above range, the foam layer has excellent shape stability and impact resistance.

  The graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiator, chain transfer agent, emulsifier, solvent, etc. used when producing the rubber-reinforced styrene resin (A12), and further the polymerization time, It can be easily controlled by adjusting the polymerization temperature and the like.

The preferable aspect of the said styrene-type resin (A1) is shown below.
(1) One or more styrene-based (co) polymers (A11).
(2) One or more kinds of rubber-reinforced styrene resin (A12).
(3) A combination of one or more styrene (co) polymers (A11) and one or more rubber-reinforced styrene resins (A12).

  The content of the styrene resin (A1) in the component (A) constituting the foamed layer is 5 to 100% by mass, preferably 30 to 100, when the component (A) is 100% by mass. The mass% is more preferably 60 to 100 mass%, still more preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass%. When the content of the styrenic resin (A1) is in the above range, the foamed layer having a high foaming ratio is excellent in foamability and fine dispersibility, the foamed cells are uniform, and the shape stability is excellent.

The said component (A) can contain another thermoplastic resin further as needed.
The amount of the other thermoplastic resin used is usually 0 to 95% by mass, preferably 0 to 70% by mass, more preferably 0 to 40% by mass, further preferably 100% by mass when the component (A) is 100% by mass. Is 0 to 20% by mass, particularly preferably 0 to 10% by mass.
The other thermoplastic resin is not particularly limited as long as it is a thermoplastic resin, and one or more of (meth) acrylic ester compounds such as polycarbonate resin (PC) and polymethyl methacrylate (PMMA) are used. Acrylic resins such as (co) polymers; vinyl chloride resins; polyamide resins (PA); polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; olefin resins; ionomers Ethylene copolymers such as ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer; polyacetal resin (POM); polyarylate resin; polyphenylene ether; polyphenylene sulfide; polytetrafluoroethylene, polyvinylidene fluoride, etc. Fluorine Fatty; Liquid crystal polymer; Imide resin; Ketone resin; Sulfone resin; Urethane resin; Polyvinyl acetate; Polyethylene oxide; Polyvinyl alcohol; Polyvinyl ether; Polyvinyl butyral; Phenoxy resin; It is done. These can be used alone or in combination of two or more. Of these, polycarbonate resins, polyester resins, thermoplastic elastomers, olefin resins, acrylic resins, vinyl chloride resins and bio-based polymers are preferred, and polycarbonate resins, polyester resins, acrylic resins and vinyl chloride polymers are preferred. A resin is more preferable.

Examples of the vinyl chloride resin include vinyl chloride homopolymer (polyvinyl chloride); polyvinylidene chloride; copolymers of vinyl chloride and other monomers copolymerizable therewith. Such other monomers include ethylene, propylene, butene, 1-pentene, butadiene, styrene, α-methylstyrene, acrylonitrile, vinylidene chloride, vinylidene cyanide, alkyl vinyl ethers, carboxylic acid vinyl esters, aryl ethers, dialkyl malees. Examples include acids, fumaric acid esters, N-vinyl pyrrolidone, vinyl pyridine, and vinyl silane.
The average degree of polymerization is usually 500 to 8,000.

  When the said component (A) consists of the said styrene resin (A1) and a vinyl chloride resin, content of the vinyl chloride resin in the said component (A) made the said component (A) 100 mass%. In this case, the content is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 40% by mass. When the content of the vinyl chloride resin is in the above range, a foamed layer having a high foaming ratio, uniform foamed cells and excellent molded appearance can be obtained.

Next, as the component (B), either a pigment or a dye may be used, or these may be combined.
As the pigment, either an organic pigment or an inorganic pigment may be used.
Examples of the organic pigment include perinone pigments; phthalocyanine pigments; quinacridone pigments; azo pigments such as permanent red, lake red, and first yellow; nitroso pigments; nitro pigments, and the like. Of these, phthalocyanine pigments and azo pigments are preferred.
Examples of inorganic pigments include oxides, sulfides, carbonates, aluminates, chromates, metal powders, and carbon black.
As the oxide, a compound containing at least one element selected from Zn, Ti, Cd, Fe, Cr, Mn, Cu, Co and Ni can be used. For example, a zinc oxide pigment such as zinc white Titanium oxide pigments such as titanium white and titanium yellow; iron oxide pigments such as FeO, FeO (OH) and Fe ₂ O ₃ (Bengara); CrO, Cr ₂ O ₃ , Cr ₂ O ₃ .2H ₂ O, etc. Chromium oxide pigments; manganese oxide pigments such as MnO, Mn ₂ O ₃ and MnO ₂ ; cobalt oxide pigments such as CuO, Cu ₂ O and CoO; CoO · Al ₂ O ₃ and Fe (Fe, Cr) ₂ O ₄ , (Co, Fe) (Fe, Cr) ₂ O ₄ , Cu (Cr, Mn) ₂ O ₄ , (Cu, Fe, Mn) (Fe, Cr, Mn) ₂ O ₄ , (Fe, Zn) (Fe, _Cr) 2 _{O 4 (Fe, Zn) Fe 2 O} 4, Co (Al, Cr) 2 O 4, Cr 2 O 3: Fe 2 O 3, (Ni, Co, Fe) (Fe, Cr) composite oxide such as 2 _{O 4} Based pigments. A calcined pigment can also be used. These can be used alone or in combination of two or more. When a compound containing at least two elements selected from Fe, Cr, Mn, Cu, Co and Ni is used, a laminate having excellent low heat storage properties can be formed.
Examples of the sulfide include iron sulfide and cadmium sulfide.
Examples of the aluminate include cobalt blue (cobalt aluminate).
Examples of chromate include lead chromate and zinc chromate.
Examples of the dye include heterocyclic dyes; anthraquinone dyes; azo dyes; perinone dyes; chlorinated dye lakes such as rhodamine lakes.

  Content of the said component (B) which comprises the said foaming layer is 0.01-15 mass parts when the quantity of the said component (A) is 100 mass parts, Preferably it is 0.05-13 mass. Part, more preferably 0.1 to 12 parts by mass. When the content of the component (B) is in the above range, it can be a foamed layer that is vividly colored and / or vividly provided with a spotted pattern, a grain pattern, or the like.

Next, the component (C) is not particularly limited as long as it contains a compound having a boiling point (atmospheric pressure) of −10 ° C. to 55 ° C. Examples of the compound include n-butane, isobutane, n-pentane, isopentane and the like. These may be included singly or in combination of two or more. By the said compound, it is excellent in foamability and the fine dispersibility of a foam cell. The content of this compound is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95-100% by mass with respect to 100% by mass of the component (C).
In addition, when the said component (C) contains several components, it is preferable that the average value of a boiling point (atmospheric pressure) is -10 degreeC-55 degreeC.

When the component (C) contains other components, hydrocarbon compounds such as ethane, cyclopentane, n-hexane, cyclohexane, etc .; methyl chloride, ethyl chloride, dichloroethane, chloroform, fluoromethane, difluoromethane, trifluoromethane, And halogenated hydrocarbons such as difluoroethane, trifluoroethane, fluorochloromethane, fluorochloroethane, dichlorodifluoromethane, and the like. These can be used alone or in combination of two or more.
The component (C) may also contain petroleum ether, carbon dioxide gas, nitrogen gas, etc., which are compounds containing oxygen atoms. The content of other components is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 0 to 5% by mass with respect to 100% by mass of the component (C).

  In the foamed layer, the content ratio of the component (C) is 0.1 to 5 parts by mass, preferably 0.2 to 4 parts by mass when the amount of the component (A) is 100 parts by mass. More preferably, it is 0.3-3 mass parts. By being in the said range, the foaming ratio of a foam layer is as high as 2 times or more, and a foam cell becomes uniform.

  The foam layer may contain an additive depending on the purpose and application. These additives include foaming aids, fillers, heat stabilizers, antioxidants, UV absorbers, anti-aging agents, antistatic agents, plasticizers, lubricants, flame retardants, antibacterial agents, antifouling agents, and fluorescent enhancement agents. Examples include whitening agents.

Examples of the foaming aid include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; halogenated hydrocarbons such as ethylene dichloride, trichloroethylene, and tetrachloroethylene; organic solvents such as esters such as ethyl acetate and butyl acetate. Can be mentioned. This foaming aid is used in combination with the above components (A) and (C) when n-propane, n-butane, isobutane, n-pentane, isopentane, cyclohexane or the like is used as the component (C). It is possible to improve the compatibility.
Content of the said foaming adjuvant is 0.1-2 mass parts normally with respect to 100 mass parts of said components (C).

Examples of the filler include talc, mica, clay, wollastonite, calcium carbonate, silica, alumina, glass fiber, glass bead, glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon balun, carbon bead, Examples thereof include carbon milled fiber, carbon black, graphite, ceramic fiber, aramid particles, aramid fiber, polyarylate fiber, various whiskers, wood flour, pulp, chaff, and paper sludge. These can be used alone or in combination of two or more.
Content of the said filler is 0.1-5 mass parts normally, when the quantity of the said component (A) is 100 mass parts.

Examples of the heat stabilizer include phosphites, hindered phenols, thioethers, and the like. These can be used alone or in combination of two or more.
Content of the said heat stabilizer is 0.01-2 mass parts normally, when the quantity of the said component (A) is 100 mass parts.

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more.
Content of the said antioxidant is 0.01-2 mass parts normally, when the quantity of the said component (A) is 100 mass parts.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more. Moreover, it may be preferable to use together with hindered amines.
Content of the said ultraviolet absorber is 0.05-2 mass parts normally, when the quantity of the said component (A) is 100 mass parts.

Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds. Thiobisphenol compound, hindered phenol compound, phosphite compound, imidazole compound, nickel dithiocarbamate salt compound, phosphate compound and the like. These can be used alone or in combination of two or more.
Content of the said anti-aging agent is 0.01-2 mass parts normally, when the quantity of the said component (A) is 100 mass parts.

Examples of the antistatic agent include a low molecular weight antistatic agent and a high molecular weight antistatic agent. Moreover, these may be an ion conduction type or an electron conduction type.
The low molecular weight antistatic agent includes an anionic antistatic agent; a cationic antistatic agent; a nonionic antistatic agent; an amphoteric antistatic agent; a complex compound; a metal alkoxide such as alkoxysilane, alkoxytitanium, alkoxyzirconium, and the like. Derivatives thereof: coated silica, phosphate, phosphate ester and the like. These can be used alone or in combination of two or more.
Examples of the polymer antistatic agent include vinyl copolymers having a sulfonic acid metal salt in the molecule, alkyl sulfonic acid metal salts, alkyl benzene sulfonic acid metal salts, and betaines. Furthermore, a polyamide elastomer, a polyester elastomer, etc. can also be used. These can be used alone or in combination of two or more.
The content of the antistatic agent is usually 0.1 to 5 parts by mass when the amount of the component (A) is 100 parts by mass.

Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate; dimethyl adipate , Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- Fatty acid esters such as (2-ethylhexyl) sebacate, diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octy Esters, trimellitic acid esters such as trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate , Tri- (2-ethylhexyl) phosphate, epoxidized soybean oil, polyether ester and the like. These can be used alone or in combination of two or more.
Content of the said plasticizer is 0.5-5 mass parts normally, when the quantity of the said component (A) is 100 mass parts.

Examples of the lubricant include fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, aliphatic Examples include alcohol, polyhydric alcohol, polyglycol, polyglycerol, metal soap, silicone, and modified silicone. These can be used alone or in combination of two or more.
Content of the said lubricant is 0.2-5 mass parts normally, when the quantity of the said component (A) is 100 mass parts.

Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.
Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, tripentyl phosphate Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds modified with these substituents, various condensed types Phosphorus ester compounds, phosphorus flame retardants such as phosphazene derivatives containing phosphorus element and nitrogen element; polytetrafluoroethylene, guanidine salts, silicone compounds, phosphazene compounds, and the like. These can be used alone or in combination of two or more.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound, and zinc stannate. These can be used alone or in combination of two or more.
Reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) , Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether and the like. These can be used alone or in combination of two or more.

Content of the said flame retardant is 0.5-30 mass parts normally, when the quantity of the said component (A) is 100 mass parts.
In addition, when making the said foaming layer contain a flame retardant, it is preferable to use a flame retardant adjuvant. As this flame retardant aid, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples thereof include ammonium polyphosphate, tin oxide, and iron oxide. These can be used alone or in combination of two or more.

Examples of the antibacterial agents include zeolite antibacterial agents such as silver zeolite and silver-zinc zeolite, silica gel antibacterial agents such as complexed silver-silica gel, glass antibacterial agents, calcium phosphate antibacterial agents, and zirconium phosphate antibacterial agents. Silicate antibacterial agents such as silver-magnesium aluminate, titanium oxide antibacterial agents, ceramic antibacterial agents, whisker antibacterial agents, etc .; formaldehyde releasing agents, halogenated aromatic compounds, road Organic antibacterial agents such as propargyl derivatives, thiocyanato compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, carboxylic acid, organometallic compounds; inorganic and organic Hybrid antibacterial agent; natural anti Agent, and the like. These can be used alone or in combination of two or more.
Content of the said antibacterial agent is 0.1-5 mass parts normally, when the quantity of the said component (A) is 100 mass parts.

The foaming layer preferably has a foaming ratio of 2 to 25 times, more preferably 2 to 20 times, and the foamed cells are uniform. The density is preferably 40 to 500 kg / m ³ , more preferably 50 to 400 kg / m ³ .
The surface of the foamed layer is smooth, and the uniform coloration and spotted pattern coloring by the component (B) are clear.
Moreover, the thickness of the said foaming layer is 0.5-25 mm normally, Preferably it is 1-25 mm, More preferably, it is 1-20 mm.

1-2. Second layer (protective layer)
This protective layer is disposed on at least one surface side of the foamed layer, and has a total light transmittance of 50% or more, preferably 60% or more, according to ASTM D1003 with respect to a test piece having a thickness of 2.5 mm. Preferably, it is a layer comprising 70% or more of the thermoplastic resin composition [Y].
Moreover, the thickness of the said protective layer is 0.01-2 mm normally, Preferably it is 0.02-1 mm, More preferably, it is 0.03-0.9 mm, More preferably, it is 0.05-0.9 mm. Therefore, if the total light transmittance of the protective layer is 50% or more, the thickness is transparent or substantially transparent. Therefore, the pattern appearing on the surface of the first layer (foamed layer) is this protective layer. Vividly recognized through the layers.
The protective layer may be provided only on one side of the foam layer (see FIG. 1) or on both sides (see FIG. 2). Moreover, it may be on the entire surface on one side or a part thereof.

  The thermoplastic resin contained in the thermoplastic resin composition [Y] is not particularly limited, but is a rubber-reinforced resin, an acrylic resin, a styrene (co) polymer, a vinyl chloride resin, a polycarbonate resin, or a polyester resin. Examples thereof include a resin and a thermoplastic elastomer. These can be used alone or in combination of two or more.

  A method for obtaining a rubber-reinforced resin having transparency is publicly known. For example, a refractive index of a rubbery polymer and a vinyl monomer polymerized in the presence of the rubbery polymer becomes a (co) polymer. The closer the refractive index is, the more transparent rubber-reinforced resin is obtained. As for the refractive index, each of the rubbery polymer and the vinyl monomer has a specific refractive index value, and the desired refractive index can be obtained by appropriately selecting the kind and amount of use.

The rubber-reinforced resin is preferably a resin obtained by polymerizing a vinyl monomer (q) containing 50% by mass or more of a (meth) acrylic acid ester compound in the presence of the rubbery polymer (p). It is.
The rubbery polymer (p) may be either a diene polymer or a non-diene polymer, such as polybutadiene and its hydrogenated product, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, isobutylene / isoprene. Copolymer, Styrene / Butadiene / Styrene Block Copolymer and its Hydrogenation, Styrene / Isoprene / Styrene Block Copolymer and Its Hydrogenation, Acrylic Rubber, Polyurethane Rubber, Silicone Rubber, Ethylene / Propylene / (Non Examples thereof include ethylene / α-olefin copolymer rubbers such as conjugated diene) copolymers and ethylene / butene-1 / (non-conjugated diene) copolymers. Among these, polybutadiene and its hydrogenated product, styrene / butadiene copolymer, hydrogenated product of styrene / butadiene / styrene block copolymer, hydrogenated product of styrene / isoprene / styrene block copolymer, acrylic rubber, And, ethylene / α-olefin copolymer rubber is preferable. When the laminate of the present invention is used in applications requiring performance such as light resistance and weather resistance, it is preferable to use the above hydrogenated product and non-diene polymer.

The weight average particle diameter of the rubbery polymer (p) is preferably 500 nm to 2,000 nm, more preferably 100 nm to 2,000 nm, still more preferably 100 nm to 1,000 nm. When the average particle diameter is in this range, the protective layer is excellent in impact resistance and transparency.
In addition, when using a rubber-reinforced resin having a high content of the rubbery polymer (p), for example, a styrene (co) polymer, a methyl methacrylate (co) polymer, another resin, etc. Used diluted. Therefore, when the thermoplastic resin composition [Y] contains a rubber-reinforced resin, the content of the rubbery polymer (p) in the thermoplastic resin composition [Y] is preferably 3 to 35% by mass, more preferably Is 5 to 30% by mass, more preferably 5 to 25% by mass. When the content of the rubber polymer (p) is in this range, the impact resistance and rigidity are excellent.

  Of the vinyl monomers (q) used for forming the rubber-reinforced resin, as the (meth) acrylic acid ester compound, a styrene-based resin that can be used as the styrene-based resin (A1) contained in the foamed layer. The (meth) acrylic acid ester compound used for forming the (co) polymer (A11) can be used. Of these, methyl methacrylate is particularly preferred.

  The content of the (meth) acrylic acid ester compound contained in the vinyl monomer (q) is 50% by mass or more, preferably 50 to 90% by mass, more preferably 55 to 80% by mass. When the content of the (meth) acrylic acid ester compound is within this range, the transparency of the protective layer is excellent. In addition, as a monomer other than the (meth) acrylic acid ester compound, an aromatic vinyl compound, a vinyl cyanide compound, a maleimide compound, or the like can be used.

  As the vinyl monomer (q), it is preferable to use a combination of a (meth) acrylic acid ester compound, an aromatic vinyl compound and a vinyl cyanide compound. By using a vinyl cyanide compound, chemical resistance can be imparted to the surface of the protective layer. In addition, when the said vinylic monomer (q) consists of a (meth) acrylic acid ester compound, an aromatic vinyl compound, and a vinyl cyanide compound, the content rate of these compounds from a viewpoint of transparency and chemical resistance. Are preferably 50 to 90% by mass, 0 to 50% by mass and 0 to 40% by mass, more preferably 55 to 90% by mass, 1 to 44% by mass and 1%, respectively, when the total is 100% by mass. It is -38 mass%.

The acrylic resin is preferably a resin obtained by using at least one (meth) acrylic acid ester compound and polymerizing a vinyl monomer containing 20% by mass or more of the compound. As a (meth) acrylic acid ester compound, a (meth) acrylic acid ester compound used for forming a styrene-based (co) polymer (A11) that can be used as the styrene-based resin (A1) contained in the foamed layer. The following examples can be applied. Of these, methyl methacrylate is preferred. As other vinyl monomers, aromatic vinyl compounds, vinyl cyanide compounds, maleimide compounds used for forming the styrene (co) polymer (A11) that can be used as the styrene resin (A1). (It may be given by post-imidization), a functional group-containing vinyl compound and the like, and may be used alone or in combination of two or more as required.
The acrylic resin is preferably a (co) polymer containing 20% by mass or more of units derived from methyl methacrylate.

  The styrenic (co) polymer (excluding the acrylic resin described above) was obtained by polymerizing a vinyl monomer having an aromatic vinyl compound content of 50% by mass or more (co). It is a polymer. As other vinyl monomers, (meth) acrylic acid ester compounds, vinyl cyanide compounds used for the formation of the styrene (co) polymer (A11) that can be used as the styrene resin (A1), A maleimide compound (which may be imparted by post-imidization), a functional group-containing vinyl compound, or the like may be used, and one or two or more are used as necessary.

  For the vinyl chloride resin that can be contained in the protective layer (thermoplastic resin composition [Y]), the vinyl chloride resin contained in the foamed layer can be applied. Moreover, about a polycarbonate resin, a polyester-type resin, and a thermoplastic elastomer, well-known resin or an elastomer can be used.

  The protective layer (thermoplastic resin composition [Y]) is a filler, heat stabilizer, antioxidant, ultraviolet absorber, anti-aging agent, antistatic agent, plasticizer, as long as the total light transmittance is not lowered. You may contain additives, such as an agent, a lubricant, a flame retardant, an antibacterial agent, an antifouling agent, a coloring agent, and a fluorescent brightening agent.

  The surface of the protective layer may be a smooth surface or may have a regular pattern or an irregular pattern by hairline processing, embossing, or the like.

1-3. Laminated body The laminated body of this invention is equipped with the said foaming layer and the said protective layer. The shape is not particularly limited and may be a planar shape (plane, curved surface), a cylindrical shape, or the like, but is preferably a film or a sheet.

Schematic diagrams of the laminate of the present invention are illustrated in FIGS.
The laminate 1 in FIG. 1 includes a foam layer 11 and a protective layer 12 disposed on the upper side in the drawing of the foam layer 11. Since the surface of the foamed layer 11 on the side bonded to the protective layer 12 is a surface that is vividly colored with a colorant and / or that clearly expresses a pattern such as a mottled pattern, it is the upper side of the drawing. Therefore, when the laminated body 1 is viewed, the pattern and the like can be easily visually recognized through the transparent protective layer 12. In addition, the thickness of the foam layer 11 and the protective layer 12 is 1-25 mm and 0.02-2 mm normally, respectively.
2 includes a foamed layer 11 and protective layers 12a and 12b disposed on both sides of the foamed layer 11. Also in this aspect, when the laminated body 1 ′ is viewed from both sides, the above-described pattern or the like can be easily visually recognized through the transparent protective layers 12a and 12b. In addition, the thickness of the foam layer 11, the protective layer 12a, and the protective layer 12b is 1-25 mm, 0.02-2 mm, and 0.02-2 mm normally, respectively.

3 includes a foam layer 11, a protective layer 12 disposed on the upper side in the drawing of the foam layer 11, and a support layer 15 disposed on the lower side in the drawing of the foam layer 11. And an adhesive layer (adhesive layer) 15.
When the laminate 1 ″ in FIG. 3 includes the support layer 15, the thicknesses of the foam layer 11 and the support layer 15 are usually 1 to 25 mm and 0.1 to 5 mm, respectively. , A layer made of a resin (composition), a layer made of another organic material, a layer made of an inorganic material, and the like.
The resin (composition) may be a thermoplastic resin (composition) or a cured resin (composition). Examples of the inorganic material include metals, alloys, oxides, carbides, nitrides, and metal salts.

When the laminate 1 ″ in FIG. 3 includes the adhesive layer 15, the thicknesses of the foam layer 11 and the adhesive layer 15 are usually 1 to 25 mm and 10 to 100 μm, respectively. The adhesive layer 15 is formed. The pressure-sensitive adhesive composition is formed by an emulsion type composition applied by a screen method, a gravure method, a mesh method, a bar coating method, or the like; an organic solvent type composition; an extrusion lamination method, a dry lamination method, a coextrusion method, or the like. There are hot-melt compositions, etc., all of which are suitable, for example, a composition containing a known acrylic polymer, diene polymer, hydrogenated diene polymer, etc. An adhesive layer can be used. A release paper or the like can be further provided on the surface of 15 (the lower side in FIG. 3) as required (not shown).
When the laminate 1 ″ in FIG. 3 includes the adhesive layer 15, the thicknesses of the foam layer 11 and the adhesive layer 15 are usually 1 to 25 mm and 10 to 100 μm, respectively. As the adhesive composition to be formed, a composition containing a known epoxy resin, phenol resin, acrylic resin, etc. can be used, and the laminate of the present invention is used immediately after the formation of the adhesive layer 15. If not, it is necessary to prevent adhesion, and the surface of the adhesive layer 15 (the lower side in FIG. 3) can be further provided with release paper or the like as necessary (not shown). )
In addition, the laminated body of this invention can be equipped with an intermediate | middle layer between the said foaming layer and the said protective layer as needed, in order to improve adhesiveness, adhesiveness, etc.

Preferred configurations of the laminate of the present invention are shown below.
[1] At least one selected from acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, and acrylonitrile / styrene / N-phenylmaleimide copolymer A thermoplastic resin comprising only a kind of styrenic (co) polymer (A11), a colorant, and at least one foaming agent selected from n-butane, isobutane, n-pentane and isopentane, In addition, the vinyl monomer (q) containing 50% by mass or more of the (meth) acrylic acid ester compound is polymerized in the presence of the foamed layer 11 having a patchy surface and the rubbery polymer (p). A laminated body comprising a protective layer 12 (or 12a and 12b) containing a rubber-reinforced resin obtained as described above, Laminate [2] from which the spotted pattern is visually recognized [2] A rubber-reinforced resin obtained by polymerizing a vinyl monomer composed of an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene polymer; A rubber-reinforced resin obtained by polymerizing a vinyl monomer comprising an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester compound in the presence of an acrylic polymer; an aromatic in the presence of an acrylic rubber Reinforced resin obtained by polymerizing vinyl monomers composed of aromatic vinyl compounds and vinyl cyanide compounds; aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid ester compounds in the presence of acrylic rubber A rubber-reinforced resin obtained by polymerizing a vinyl monomer comprising: an aromatic vinyl compound and vinyl cyanide in the presence of an ethylene / α-olefin copolymer rubber. A rubber-reinforced resin obtained by polymerizing a vinyl monomer composed of a vinyl compound; and an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acryl in the presence of an ethylene / α-olefin copolymer rubber. A thermoplastic resin comprising only at least one rubber-reinforced resin (A12) selected from a rubber-reinforced resin obtained by polymerizing a vinyl monomer comprising an acid ester compound, a colorant, and n-butane In the presence of a foamed layer 11 containing at least one foaming agent selected from isobutane, n-pentane and isopentane, and having a patchy surface, and a rubbery polymer (p), A protective layer 12 (or 12a and 12b) containing a rubber-reinforced resin obtained by polymerizing a vinyl monomer (q) containing 50% by mass or more of a (meth) acrylic ester compound is provided. A laminated body in which spots are visible from the surface side of the protective layer [3] one or more of the styrene-based (co) polymers (A11) in the above aspect [1], and the above aspect [ 2] containing a thermoplastic resin comprising at least one rubber-reinforced resin (A12), a colorant, and at least one foaming agent selected from n-butane, isobutane, n-pentane and isopentane. And a vinyl monomer (q) containing 50% by mass or more of a (meth) acrylic acid ester compound in the presence of the foam layer 11 having a patchy surface and the rubbery polymer (p). A laminate comprising a protective layer 12 (or 12a and 12b) containing a rubber-reinforced resin obtained by polymerization, wherein the spotted pattern is visible from the surface side of the protective layer [4] Smell in any one of embodiments [1] to [3] The thermoplastic resin constituting the foam layer 11 further contains at least one selected from polycarbonate resin, polyester resin, thermoplastic elastomer, olefin resin, acrylic resin, vinyl chloride resin, and biobase polymer. And a vinyl monomer (q) containing 50% by mass or more of a (meth) acrylic acid ester compound in the presence of the foam layer 11 having a patchy surface and the rubbery polymer (p). A laminate comprising a protective layer 12 (or 12a and 12b) containing a rubber-reinforced resin obtained by polymerizing the above-mentioned laminate, wherein a spotted pattern is visually recognized from the surface side of the protective layer [1 The rubbery polymer (p) in [4] to [4] is preferably a diene rubber polymer, a hydrogenated diene rubber polymer, and an acrylic rubber.

2. The manufacturing method of a laminated body of this invention is equivalent to 0-50 mass% of the thermoplastic resin equivalent to 5-50 mass% of the said thermoplastic resin (A), and the said coloring agent (B). The composition [X1] containing the coloring agent to be used and the foaming agent corresponding to 20 to 100% by mass of the foaming agent (C), and 50 to 95% by mass of the thermoplastic resin (A). A composition [X2] containing a thermoplastic resin, a colorant corresponding to 50 to 100% by mass of the colorant (B), and a foaming agent corresponding to 0 to 80% by mass of the foaming agent (C). And a thermoplastic resin composition [Y] having a total light transmittance of 50% or more according to ASTM D1003 for a test piece having a thickness of 2.5 mm It is characterized by including the process to do.

The composition [X1] constituting the thermoplastic resin composition [X] is referred to as a thermoplastic resin (hereinafter referred to as “resin (AX1)”) corresponding to 5 to 50% by mass of the thermoplastic resin (A). ), A colorant corresponding to 0 to 50% by mass of the colorant (B) (hereinafter referred to as “colorant (BX1)”), and 20 to 100% by mass of the foaming agent (C). It is a composition containing a foaming agent (hereinafter referred to as “foaming agent (CX1)”). The composition [X1] may be a master batch pellet having a uniform composition (consisting of only one kind) or a mixture of two or more master batch pellets having different compositions. In the latter case, each composition such as two or more kinds of master batch pellets is selected so that the above-mentioned components have a predetermined content ratio as a whole of the composition [X1].
On the other hand, the composition [X2] comprises a thermoplastic resin corresponding to 50 to 95% by mass of the thermoplastic resin (A) (hereinafter referred to as “resin (AX2)”) and the colorant (B). A colorant corresponding to 50 to 100% by mass (hereinafter referred to as “colorant (BX2)”) and a foaming agent corresponding to 0 to 80% by mass of the foaming agent (C) (hereinafter referred to as “foaming agent (CX2)”. ) ").)). The composition [X2] may also be a master batch pellet of uniform composition (consisting of only one type) or a mixture of two or more master batch pellets having different compositions. In the latter case, each composition such as two or more kinds of master batch pellets is selected so that the above-mentioned components have a predetermined content ratio as a whole of the composition [X2]. For example, a mixture of a master batch pellet (M1) made of a resin composition containing a small amount of a colorant and a master batch pellet (M2) made of a resin composition containing a large amount of a colorant is used as the composition [X2]. Can be used. In this case, if the composition of the composition [X2] is satisfied by the master batch pellet (M1) and the master batch pellet (M2), the composition of the master batch pellet (M1) does not satisfy the composition of the composition [X2]. May be.
In each component included in the composition [X1] and [X2], the resin (AX1) and the resin (AX2) constitute the thermoplastic resin (A), and the colorant (BX1) and the colorant (BX2). The colorant (B) is constituted by the above, and the foaming agent (C) is constituted by the foaming agent (CX1) and the foaming agent (CX2).

The resin (AX1) contained in the composition [X1] may be only the styrene resin (A1), may be only another thermoplastic resin, may be the styrene resin (A1), and other A combination of thermoplastic resins may also be used. Preferably, only the styrene resin (A1), that is, the styrene (co) polymer (A11) and / or the rubber-reinforced styrene resin (A12).
Similarly, the resin (AX2) contained in the composition [X2] may be only the styrene resin (A1), may be only other thermoplastic resin, or may be the styrene resin (A1). ) And other thermoplastic resins. Preferably, the styrene resin (A1) alone, and the styrene resin (A1) and other thermoplastic resins are used in combination. In addition, in the said composition [X1] and [X2], when using only another thermoplastic resin, it is restricted to any one of composition [X1] and [X2].

In addition, the laminate has a foaming ratio as high as 2 times or more, is lightweight, has no distortion, has excellent smoothness, and has a clear pattern appearing on the foamed layer formed of the thermoplastic resin composition [X]. A preferred configuration for obtaining is shown below.
As described above, the mass ratios of the resin (AX1) contained in the composition [X1] and the resin (AX2) contained in the composition [X2] are 5 to 50% by mass and 50%, respectively. It is -95 mass%, More preferably, it is 7-45 mass% and 55-93 mass%, More preferably, it is 10-40 mass% and 60-90 mass%.
In addition, when the said composition [X1] contains a styrene resin (A1), the structure of the acetone soluble component obtained by immersing this styrene resin (A1) in acetone is 100 mass in whole. %, A monomer unit derived from an aromatic vinyl compound, a monomer unit derived from a vinyl cyanide compound, and a monomer unit derived from another compound are each preferably from 75 to They are 95 mass%, 5-25 mass%, and 0-20 mass%, More preferably, they are 80-87 mass%, 13-20 mass%, and 0-7 mass%. By setting it as this range, the foaming layer excellent in coloring property is obtained, and it is excellent in external appearance property.

As described above, the mass ratio of the colorant (BX1) contained in the composition [X1] and the colorant (BX2) contained in the composition [X2] is 0 to 50% by mass, respectively. And 50 to 100 mass%, more preferably 0 to 40 mass% and 60 to 100 mass%, still more preferably 0 to 20 mass% and 80 to 100 mass%.
Moreover, the foaming agent (CX1) contained in the said composition [X1] and the mass ratio of the foaming agent (CX2) contained in the said composition [X2] are 20-100 respectively as above-mentioned. They are mass% and 0-80 mass%, More preferably, they are 50-100 mass% and 0-50 mass%, More preferably, they are 70-100 mass% and 0-30 mass%.
By preparing compositions [X1] and [X2] within the above range and mixing them into a thermoplastic resin composition [X], the foaming ratio is as high as 2 times or more, and foaming is performed on the surface. A foam layer having uniform cells and excellent molded appearance can be easily obtained.

A particularly preferred combination of the above compositions [X1] and [X2] is that the composition [X1] comprises a composition of the acetone-soluble component in the styrene resin (A1) contained therein, and a colorant (BX1). Is a foaming agent-containing composition in which the mass proportion of the foaming agent (CX1) is 100 mass% with respect to the entire foaming agent (C). And the composition [X2] has a mass ratio of the colorant (BX2) of 80 to 100% by mass with respect to the entire colorant (B) and does not contain the foaming agent (CX2). It is the aspect which is a containing composition. The composition [X1] is preferably a foaming agent-containing master batch pellet having an expansion ratio of 1.15 or less, more preferably 1.10 or less. On the other hand, the composition [X2] is preferably a colorant-containing master batch pellet that does not contain the foaming agent (C).
Examples of the coloring of the foamed layer in the present invention include uniform coloring and spotted pattern coloring. Uniform coloring can be achieved by appropriately selecting conditions such that the colorant (B) is uniformly dispersed. On the other hand, spot pattern coloring can be achieved by appropriately selecting conditions that make it difficult to disperse a part of the colorant (B). In the examples described later, specific examples of spotted pattern coloring are shown, but when a pellet mixture obtained by simply mixing three kinds of pellets is directly supplied as a molding material to a molding machine to produce a molded product. Due to poor dispersion of some of the colorant (B), the pattern is colored. Other methods for increasing the colorant dispersion failure include a method of using a resin having a high melting temperature as a resin used in the colorant-containing master batch pellet, a method of increasing the amount of lubricant used, and the like. In addition, when the above three kinds of pellet mixture are melt-kneaded and used as a molding material and supplied to a molding machine to produce a molded product, uniform coloring is achieved by uniformly dispersing the colorant by melt-kneading the pellet mixture. It becomes.
In addition, said composition [X1] and [X2] are foaming adjuvant, a filler, a heat stabilizer, antioxidant, an ultraviolet-ray inhibitor, anti-aging agent, antistatic which were illustrated above as needed. An additive such as an agent, a plasticizer, a lubricant, a flame retardant, an antibacterial agent, an antifouling agent, a fluorescent brightener, and a fluorescent dye may be included.

  The foaming agent-containing master batch pellet as the composition [X1] is preferably a melt-kneaded product produced by blending and kneading the foaming agent (C) while keeping the resin (AX1) in a molten state. . For example, a step of melt-kneading the resin (AX1) (hereinafter referred to as “melting step”), a molten resin (AX1) obtained by the melting step, a foaming agent (C) or a foaming agent (C ) And a foaming auxiliary agent, a step of melt-kneading the mixture (hereinafter referred to as “kneading step”), the kneaded product obtained by the kneading step is used as a linear body, and the linear body is immediately cooled. It can be produced by a manufacturing method in which a step (hereinafter referred to as “cooling step”) and a step of cutting the cooled linear body (hereinafter referred to as “cutting step”) are sequentially performed.

In the melting step, the resin (AX1) is melt-kneaded at a melting temperature or higher using an extruder such as a single-screw extruder, a twin-screw extruder, or a tandem extruder.
Thereafter, in the kneading step, the extruder used in the melting step or the above-exemplified extruder prepared separately is used, and the foaming agent liquefied in the molten resin (AX1) ( C), or the liquefied foaming agent (C) and the foaming aid are supplied and usually melt kneaded at a temperature equal to or higher than the melting temperature of the resin (AX1).

Next, in the cooling step, the kneaded product obtained in the kneading step is extruded from an extrusion hole having a diameter of 1 to 5 mm, for example, disposed at the exit of the extruder to form a continuous linear body or the like. To do. Then, the extruded linear body is introduced into a coolant such as water and cooled.
Then, the foamed agent containing masterbatch pellet of a desired magnitude | size can be manufactured by cut | disconnecting the cooled linear body to suitable length.

The shape and size of the foaming agent-containing master batch pellet are not particularly limited, and the shape is, for example, flat (circular, square, etc.), columnar (cylinder, prism, etc.), linear, indefinite shape, etc. Can do.
On the other hand, the shape and size of the molten mixture are not particularly limited, and the shape is, for example, powdery, spherical, substantially spherical, flat (circular, square, etc.), columnar (cylinder, prism, etc.), linear, indefinite. It can be a shape or the like.

  In the production of the laminate, the description of the thermoplastic resin composition [Y] in the protective layer can be applied as it is to the thermoplastic resin composition [Y] used in combination with the thermoplastic resin composition [X]. it can.

  In the method for producing a laminate of the present invention, the thermoplastic resin compositions [X] and [Y] are usually in a molten state by a single-screw extruder, a twin-screw extruder, a tandem extruder, or the like, respectively. Thereafter, it is coextruded. Thereby, the laminated body which the foaming layer and the protective layer joined is manufactured (refer FIG.1 and FIG.2).

  The laminate of the present invention can be used as an alternative to wooden products, for example, civil engineering / construction related materials such as display boards; interior / exterior related materials for vehicles; electrical / electronic parts; sports equipment; walls, floors, frames, furniture (desks) Drawers, top boards, etc.), decorative sheets, partitions, lattices, fences, gutters, sizing boards, carports, terraces, decks, bathroom components (counters, doors, apron, UB frames, window frames, shelves, etc.), kitchen Suitable for housing and office interior and exterior materials such as members (doors, partition plates, window frames, shelves, etc.); toys; cushioning materials such as game machines, reinforcing materials, heat insulating materials, core materials, substitute plywood, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Raw material components Components used in the following Examples and Comparative Examples are shown.

1-1. Thermoplastic resin A
Styrenic resins (A-1) to (A-7) shown below were used.
(1) Styrenic resin (A-1)
An acrylonitrile / styrene copolymer having a styrene unit amount of 79% and an acrylonitrile unit amount of 21%. The weight average molecular weight (Mw) is 160,000. Soluble in acetone.
(2) Styrenic resin (A-2)
An acrylonitrile / styrene copolymer having a styrene unit amount of 84% and an acrylonitrile unit amount of 16%. Mw is 150,000. Soluble in acetone.
(3) Styrenic resin (A-3)
An acrylonitrile / styrene copolymer having a styrene unit amount of 70% and an acrylonitrile unit amount of 30%. Mw is 200,000. Soluble in acetone.

(4) Styrenic resin (A-4)
A rubber-reinforced resin obtained by emulsion polymerization of styrene and acrylonitrile in the presence of polybutadiene rubber particles having a volume average particle diameter of 280 nm and a toluene-insoluble content of 80%. The rubber-reinforced resin has a graft ratio of 55%, a polybutadiene rubber content of 51%, a styrene unit amount of 35%, and an acrylonitrile unit amount of 14%.
(5) Styrenic resin (A-5)
A rubber-reinforced resin obtained by emulsion polymerization of styrene and acrylonitrile in the presence of an acrylic copolymer rubber comprising 99% n-butyl acrylate units and 1% allyl methacrylate units. The rubber-reinforced resin has a graft ratio of 60%, an acrylic copolymer rubber content of 50.8%, a styrene unit amount of 36.4%, and an acrylonitrile unit amount of 12.8%. The intrinsic viscosity of the acetonitrile-soluble component (measured in methyl ethyl ketone at 30 ° C.) is 0.55 dl / g.

(6) Styrenic resin (A-6)
An acrylonitrile / styrene / methyl methacrylate copolymer having a styrene unit amount of 21%, an acrylonitrile unit amount of 7% and a methyl methacrylate unit amount of 72%. The intrinsic viscosity of the acetone-soluble component (measured in methyl ethyl ketone at 30 ° C.) is 0.5 dl / g.
(7) Styrene resin (A-7)
The α-methylstyrene / acrylonitrile copolymer has an α-methylstyrene unit content of 73% and an acrylonitrile unit content of 27%.

1-2. Colorant B
(1) B-1
A composite oxide of Fe and Cr (trade name “Fellow Color 42-703A”, manufactured by Nippon Fellow) was used. Black colorant.
(2) B-2
A composite oxide of Fe and Mn (trade name “Fellow Color 42-350A”, manufactured by Nippon Fellow) was used. It is a yellow colorant.
(3) B-3
A composite oxide of Cu, Cr and Mn (trade name “Fellow Color 42-303B”, manufactured by Nippon Fellow) was used. Brown colorant.

1-3. Foaming agent C
Butane (boiling point at atmospheric pressure—0.5 ° C.) was used.
1-4. Chemical foaming agent D
An endothermic decomposition type foaming agent (trade name “SELBON SC-P”, manufactured by Eiwa Kasei Co., Ltd.) whose main component is sodium hydrogen carbonate was used.
1-5. Lubricant E
Magnesium stearate was used.

2. Thermoplastic resin composition for forming a foam layer [X]
A foaming agent-containing master batch pellet and a colorant-containing master batch pellet were prepared as follows to obtain a thermoplastic resin composition for forming a foam layer.

2-1. Master batch pellets containing foaming agent [X1]
Production Example 1 [Production of foaming agent-containing master batch pellet (X1-1)]
100 parts of styrene resin (A-1) was supplied to a single screw extruder having a screw diameter of 40 mm and the cylinder temperature set to 170 ° C. to 250 ° C. to melt it. Thereafter, 4.5 parts of the foaming agent C was supplied from the above-mentioned extruder cylinder intermediate inlet and melt-kneaded.
Subsequently, it was made into a strand through a 5-hole (2.5 mmφ / hole) die disposed at the outlet of the extruder and directly introduced into the water tank. After cooling in a water tank, it was cut into a length of 3 mm to obtain a foaming agent-containing master batch pellet (X1-1) having an outer diameter of about 2 mm.

When the content of the foaming agent C and the expansion ratio in the foaming agent-containing master batch pellet (X1-1) were measured by the following method, the composition of the foaming agent-containing master batch pellet (X1-1) is shown in Table 1. The result was obtained.
[Butane content measurement method]
About 10 g of the foaming agent-containing master batch pellet was placed on a 200 ° C. hot plate, heated for 5 minutes, weighed accurately before and after heating, and the difference was defined as the butane content.
[Foaming ratio]
The mass calculated value W1 was calculated from the bulk volume and the specific gravity of the resin obtained from the external dimensions of the foaming agent-containing master batch pellet, and the ratio between the W1 and the mass measured value W2 was defined as the expansion ratio.
Foaming magnification (times) = W1 / W2
The specific gravity of the resin used for the calculation is acrylonitrile / styrene copolymer; 1.08 g / cm ³ .

Production Examples 2 to 3 [Production of foaming agent-containing master batch pellets (X1-2) to (X1-3)]
Except having used styrene-type resin (A-2)-(A-3) and the foaming agent C in the ratio shown in Table 1, respectively, it was carried out similarly to manufacture example 1, and a foaming agent containing masterbatch pellet (X1-2) ) To (X1-3) were produced and subjected to various evaluations. The results are shown in Table 1.
Moreover, the masterbatch pellet (X1-4) which consists only of styrene resin (A-2) which does not contain the foaming agent C was manufactured similarly (refer manufacture example 4, Table 1).

2-2. Master batch pellets containing colorant [X2]
Production Example 5 [Production of colorant-containing masterbatch pellet (X2-1)]
Styrenic resins (A-4) and (A-6) are 30 parts and 70 parts, respectively, and colorants (B-1) and (B-2) are 0.07 parts and 0.03, respectively. Part and 0.7 part of lubricant E were put into a Henschel mixer and mixed for 2 minutes to obtain a mixture. Then, this mixture was supplied to a single screw extruder with a screw diameter of 40 mm set at a cylinder temperature of 170 ° C. to 250 ° C., and melt kneaded. The solution was made into a strand through a 5-hole (2.5 mmφ / hole) die disposed at the outlet of the extruder and directly introduced into the water tank. After cooling in the water tank, it was cut into a length of 3 mm to obtain a colorant-containing master batch pellet (X2-1) having an outer diameter of about 2 mm (see Table 2).

Production Example 6 [Production of Colorant-Containing Master Batch Pellet (X2-2)]
Styrenic resins (A-5) and (A-6) are 30 parts and 70 parts, respectively, and colorants (B-1) and (B-2) are 0.07 parts and 0.03, respectively. Part No. and 0.7 part of lubricant E were used in the same manner as in Production Example 5 to obtain a colorant-containing master batch pellet (X2-2) (see Table 2).

Production Example 7 [Production of Colorant-Containing Master Batch Pellet (X2-3)]
Styrenic resins (A-4), (A-5) and (A-7) are respectively 4 parts, 6 parts and 37 parts, and colorants (B-1), (B-2) and (B -3), respectively, except that 25 parts, 2 parts and 25 parts and 1 part of lubricant E were used, respectively, to obtain a colorant-containing master batch pellet (X2-3) in the same manner as in Production Example 5. (See Table 2).

2-3. Preparation of Thermoplastic Resin Composition [X] for Foam Layer Formation Preparation Example 1
25 parts of foaming agent-containing master batch pellet (X1-1), 71 parts of colorant-containing master batch pellet (X2-2) and 4 parts of (X2-3) are put into a Henschel mixer and mixed for 2 minutes. A foamed layer-forming thermoplastic resin composition for Example 1 was prepared (see the “Formulation (part)” column in Table 3). Further, the composition of the obtained thermoplastic resin composition for forming a foamed layer, that is, the content ratio of the colorant B and the like when the thermoplastic resin A is 100 parts, is shown in Table 3, “Composition of foamed layer ( Part) ”column.

Preparation Examples 2-7 and 9
Foaming for Examples 2 to 7 and Comparative Example 2 using the foaming agent-containing masterbatch pellets and the colorant-containing masterbatch pellets described in the “Formulation (part)” column of Table 3 in the same manner as in Preparation Example 1. A layer-forming thermoplastic resin composition was prepared (see Table 3).

Preparation Example 8
24.05 parts of master batch pellet (X1-4) not containing foaming agent C, 71 parts of colorant-containing master batch pellet (X2-2) and 0.95 part of chemical foaming agent D were charged into a Henschel mixer, By mixing for 2 minutes, a thermoplastic resin composition for forming a foam layer for Comparative Example 1 was prepared (see the “Formulation (part)” column in Table 3).

3. Protective layer forming thermoplastic resin composition [Y]
(1) Y-1
In the presence of an acrylic copolymer rubber, which is a copolymer comprising 60% n-butyl acrylate unit, 20% butadiene unit, 19% styrene unit, and 1% allyl methacrylate unit, methacrylic acid is present. A rubber reinforced resin obtained by emulsion polymerization of methyl, styrene and acrylonitrile was used as the thermoplastic resin composition (Y-1). The rubber-reinforced resin has a graft ratio of 55%, an acrylic copolymer rubber content of 15%, a methyl methacrylate unit amount of 56%, a styrene unit amount of 11%, and an acrylonitrile unit amount of 7%. The intrinsic viscosity of the acetonitrile-soluble component (measured in methyl ethyl ketone at 30 ° C.) is 0.5 dl / g. The rubber reinforced resin was kneaded at 210 ° C. using a single screw extruder with a screw diameter of 40 mm to be pelletized. The total light transmittance of this thermoplastic resin composition (Y-1) is 75%.
(2) Y-2
A rubber-reinforced resin obtained by emulsion polymerization of methyl methacrylate, styrene and acrylonitrile in the presence of a polybutadiene rubber having a volume average particle size of 280 nm and a toluene insoluble content of 80% is used as a thermoplastic resin composition (Y-2). It was. The rubber-reinforced resin has a graft ratio of 55%, a polybutadiene rubber content of 20%, a methyl methacrylate unit amount of 56%, a styrene unit amount of 18%, and an acrylonitrile unit amount of 6%. The intrinsic viscosity of acetone-soluble components (measured in methyl ethyl ketone at 30 ° C.) is 0.5 dl / g. The rubber reinforced resin was kneaded at 210 ° C. using a single screw extruder with a screw diameter of 40 mm to be pelletized. The total light transmittance of this thermoplastic resin composition (Y-2) is 88%.
(3) Y-3
A rubber reinforced resin obtained by solution polymerization of methyl methacrylate, styrene and acrylonitrile in the presence of hydrogenated block copolymer rubber (trade name “Dynalon 4600P” manufactured by JSR Corporation) is used as a thermoplastic resin composition (Y -3). This rubber reinforced resin has a graft ratio of 42%, a hydrogenated block copolymer rubber content of 20%, a methyl methacrylate unit amount of 57%, a styrene unit amount of 11.5%, and an acrylonitrile unit amount of 11.5. %. The intrinsic viscosity of acetone-soluble components (measured in methyl ethyl ketone at 30 ° C.) is 0.5 dl / g. The rubber reinforced resin was kneaded at 210 ° C. using a single screw extruder with a screw diameter of 40 mm to be pelletized. The total light transmittance of this thermoplastic resin composition (Y-3) is 79%.
(4) Y-4
100 parts of vinyl chloride resin having an average polymerization degree of 1050, 32 parts of DIDP (diisodecyl phthalate, plasticizer), 7 parts of epoxidized soybean oil (plasticizer), DOZ (dioctyl azelate, plasticizer), liquid Ba- A thermoplastic resin composition (Y-4) obtained by mixing 3 parts of Cd—Zn composite (stabilizer) and 0.25 parts of mineral oil (lubricant) was used. The total light transmittance of this composition is 79%.

4). Example 1 Production of Laminate and Its Evaluation
Using 100 parts of the thermoplastic resin composition for forming a foam layer obtained in Preparation Example 1 and 100 parts of the thermoplastic resin composition for forming a protective layer (Y-1), co-extrusion was performed under the following conditions to obtain foam. 50 mm width provided with a foam layer (3 mm thickness) colored in a patch pattern by a thermoplastic resin composition for layer formation and a transparent protective layer (0.2 mm thickness) by a thermoplastic resin composition for protective layer formation (A long two-layer laminate sheet) was obtained (see Table 3).
<Production conditions>
The thermoplastic resin composition for forming the foamed layer uses a single screw extruder with a screw diameter of 40 mm, the screw rotation speed is 20 rpm, the melt kneading temperature is 200 ° C., the take-up speed is 0.85 m / min, and the protective layer The forming thermoplastic resin composition was co-extruded using a single screw extruder with a screw diameter of 20 mm, a screw rotation speed of 30 rpm, a melt kneading temperature of 220 ° C., and a take-up speed of 0.85 m / min to obtain a laminate. It was.

Examples 2-7
Using the thermoplastic resin composition for forming a foam layer and the thermoplastic resin composition for forming a protective layer shown in Table 3, a laminate (elongated two-layer laminate sheet) was obtained in the same manner as in Example 1. (See Table 3).
In Example 7 using the protective layer-forming thermoplastic resin composition (Y-4), the melt-kneading temperature was 200 ° C.

Example 8
Instead of using a foaming agent-containing masterbatch pellet and a colorant-containing masterbatch pellet as the thermoplastic resin composition for forming a foaming layer, a foaming agent-containing thermoplastic resin body (of 102.6 parts) obtained by the following method was used. 100 parts), and further using 100 parts of the protective layer-forming thermoplastic resin composition (Y-1) in the same manner as in Example 1 to obtain a laminate (long two-layer laminate sheet). It was.
First, 23 parts of styrene resin (A-1), 22.5 parts of styrene resin (A-5), 52.5 parts of styrene resin (A-6), and colorant (B-1) 1 Part, 0.1 part of the colorant (B-2), 1 part of the colorant (B-3) and 0.5 part of the lubricant E are mixed with a Henschel mixer, and the single screw extrusion with a screw diameter of 40 mm is performed. It was melted at 200 ° C. using a machine. Thereafter, 2 parts of the foaming agent C was supplied from the injection port at the rear of the extruder and melt-kneaded to obtain a foaming agent-containing thermoplastic resin body (102.6 parts).

Comparative Example 1
Using the thermoplastic resin composition for forming a foam layer and the thermoplastic resin composition for forming a protective layer shown in Table 3, a laminate (elongated two-layer laminate sheet) was obtained in the same manner as in Example 1. (See Table 3).

Comparative Example 2
Using only the thermoplastic resin composition for forming a foam layer, a monolayer sheet consisting only of the foam layer was obtained under the production conditions in Example 1.

The following evaluation was performed about the obtained laminated body (elongate 2 layer type | mold laminated sheet). The results are also shown in Table 3.
(1) Foaming ratio of the foam layer From the bulk volume and the specific gravity of the resin determined from the outer dimensions of the foam layer, a calculated mass value W1 is calculated, and the ratio between this W1 and the measured mass value W2 is defined as the foaming ratio. did.
Foaming magnification (times) = W1 / W2

(2) Appearance The colorability and smoothness of the obtained laminate were visually observed.
<Colorability>
◎; The spotted pattern was clearly visible through the protective layer.
○: The sharpness of the mottled pattern is slightly inferior through the protective layer.
Δ: The sharpness of the mottled pattern is slightly inferior through the protective layer.
X: The clearness of the mottled pattern was inferior through the protective layer.
<Smoothness>
A: A two-layer laminated sheet having no distortion was obtained, and the surface thereof was smooth.
Δ: A two-layer laminated sheet having no distortion was obtained, but a non-smooth portion was observed on a part of the surface.
X: A slightly distorted two-layer laminate sheet was obtained, and irregularities were found on a part of the foam layer surface on the side without the protective layer.

From Table 3, Examples 1-7 were excellent in the sharpness of the spot pattern, and excellent in smoothness. Conventionally, the patch pattern colorability of the non-diene rubber reinforced resin foam was inferior to that of the diene rubber reinforced resin, but by using the physical foaming agent of the present invention, it is equivalent to the diene rubber reinforced resin. Spotted pattern colorability could be achieved.
On the other hand, Comparative Example 1 is an example in which a chemical foaming agent outside the scope of the present invention was used, and spotted pattern colorability and smoothness were inferior. Moreover, although the comparative example 2 is a single layer sheet | seat which does not have a protective layer and consists only of a foaming layer, compared with the laminated body of an Example, it was inferior in the spot pattern coloring property and smoothness. This means that the protective layer contributes to the improvement of spot pattern colorability and smoothness.

  The laminate of the present invention includes civil engineering / construction related materials such as display boards; interior and exterior related materials for vehicles; electrical / electronic parts; sports equipment; walls, floors, frames, furniture (desk drawers, top plates, etc.), makeup Sheets, partitions, lattices, fences, gutters, sizing boards, carports, terraces, decks, bathroom components (counters, doors, apron, UB frames, window frames, shelves, etc.), kitchen components (doors, dividers, window frames) It is suitable for interior / exterior materials for houses and offices such as shelves, etc .; toys; cushioning materials such as game machines, reinforcing materials, heat insulating materials, core materials, substitute plywood and the like.

It is the schematic which shows an example of the cross-section of the laminated body (laminated sheet etc.) of this invention. It is the schematic which shows the other example of the cross-section of the laminated body (laminated sheet etc.) of this invention. It is the schematic which shows the other example of the cross-section of the laminated body (laminated sheet etc.) of this invention.

Explanation of symbols

1, 1 ′ and 1 ″; laminate 11; first layer (foamed layer)
12, 12a and 12b; second layer (protective layer)
15: Support layer or adhesive layer (adhesive layer)

Claims (9)

  (A) When the whole is 100% by mass, a thermoplastic resin containing 5 to 100% by mass of a styrene resin, (B) a colorant, and (C) a compound having a boiling point of −10 ° C. to 55 ° C. The content of the colorant (B) and the foaming agent (C) is 0.01 to 15 parts by weight and 0 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), respectively. A first layer made of a foam of 1 to 5 parts by mass, and a total light transmission according to ASTM D1003 with respect to a test piece of 2.5 mm thickness disposed on at least one side of the first layer And a second layer made of a thermoplastic resin composition [Y] having a rate of 50% or more.   The laminate according to claim 1, wherein the surface of the first layer has a spotted pattern.   The said thermoplastic resin composition [Y] contains at least 1 sort (s) chosen from rubber reinforced resin, polycarbonate resin, polyester resin, thermoplastic elastomer, acrylic resin, and vinyl chloride resin. Laminated body. The laminate according to any one of claims 1 to ³ , wherein the density of the first layer is 40 to 500 kg / m ³ .   The laminate according to any one of claims 1 to 4, which is a film or a sheet.   The laminate according to any one of claims 1 to 5, which is used as a substitute for a wooden product. It is a manufacturing method of the layered product according to any one of claims 1 to 6,
A thermoplastic resin corresponding to 5 to 50% by mass of the thermoplastic resin (A), a colorant corresponding to 0 to 50% by mass of the colorant (B), and 20 to 100 of the foaming agent (C). Composition [X1] containing a foaming agent corresponding to mass%, a thermoplastic resin corresponding to 50 to 95 mass% of the thermoplastic resin (A), and 50 to 100 of the colorant (B). A thermoplastic resin composition [X] comprising a composition [X2] containing a colorant corresponding to mass% and a foaming agent corresponding to 0 to 80 mass% of the foaming agent (C);
A laminate comprising a step of co-extruding a test piece having a thickness of 2.5 mm with a thermoplastic resin composition [Y] having a total light transmittance of 50% or more according to ASTM D1003. Production method.   The method for producing a laminate according to claim 7, wherein the composition [X1] is a foaming agent-containing masterbatch having an expansion ratio of 1.15 or less.   When the acetone-soluble component obtained by immersing the styrene-based resin contained in the composition [X1] in acetone is 100% by mass as a whole, monomer unit 75 composed of an aromatic vinyl compound is used. The composition according to claim 7 or 8, which is constituted by ~ 95% by mass, 5-25% by mass of a monomer unit composed of a vinyl cyanide compound, and 0-20% by mass of a monomer unit composed of another compound. A manufacturing method of a layered product.

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