JP2002292796A - Decorative panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative panel excellent in transparency, color developability, weatherability, flexibility, durability, elasticity restoring properties and soft feeling. SOLUTION: The decorative panel is constituted by laminating a layer (a) comprising multilayered structural polymer particles and a layer (b) comprising other component. The multilayered structural polymer particles has a rubber component layer (I) formed by copolymerizing a monomer mixture containing acrylic ester and a polyfunctional monomer and a thermoplastic resin component layer (II) formed by polymerizing a monomer consisting of methacrylic ester and other monomer as an arbitrary component and satisfy such a condition that, (1) the number average mol.wt. of the thermoplastic resin component constituting the outermost layer is not more than 30,000, (2) a mass ratio of layer (I)/layer (II) is 30/70-90/10, and (3) an average particle size is not more than 150 nm. The other component is selected from other thermoplastic resin, a thermosetting resin, vulcanized rubber, glass, a metal, gypsum, concrete, wood, particle board and paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative board having a layer comprising specific multi-layer polymer particles. More specifically, a specific multilayer structure polymer which is excellent in transparency, color development, weather resistance, flexibility, durability, elastic recovery, soft texture, and is suitably used as decorative steel plate, wallpaper, and other decorative plates. The present invention relates to a decorative board obtained by laminating a layer composed of particles and a layer composed of other components.

[0002]

2. Description of the Related Art Conventionally, decorative boards which include a polyvinyl chloride resin layer have been known, such as ceiling materials, wall materials, and floor materials for hospitals, restaurants, offices, factories, vehicles, and general homes. It is used for A decorative board or wallpaper using a vinyl chloride resin has poor weather resistance, and even if it is used indoors, it cannot be denied that it is deteriorated by ultraviolet rays generated from a fluorescent lamp. Further, there is a problem that the plasticizer used in the polyvinyl chloride resin bleeds on the surface of the decorative board or the wallpaper. Dust adheres to the bleeding plasticizer, and the decorative board or wallpaper using the vinyl chloride resin is easily stained. In this way, the decorative board or wallpaper using the vinyl chloride resin is easily stained and has poor durability, so it is frequently replaced.
Due to the problem of environmental load during incineration, alternative materials for vinyl chloride resin are required. On the other hand, a durable wallpaper in which an acrylic resin film is laminated on a vinyl chloride resin wallpaper is known. Although the durability of such a wallpaper is improved, its flexibility and elastic recovery are poor, and it is not satisfactory.

[0003]

DISCLOSURE OF THE INVENTION The present invention is excellent in transparency, color development, weather resistance, flexibility, elastic recovery, soft texture, durability for long-term use, and plasticizer. An object of the present invention is to provide a decorative board which is free from bleed contamination and has a small environmental load when incinerated and disposed of.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, as a result of diligent studies, it has been found that a decorative plate obtained by laminating a layer composed of a specific multi-layered polymer particle and a layer composed of other components is described above. The inventors have found that the problem can be solved, and have completed the present invention.

[0005] That is, the present invention is a decorative plate comprising at least one layer composed of multilayer polymer particles and at least one layer composed of other components laminated on each other. (1) Multilayer polymer particles comprising two or more layers having at least one rubber component layer (I) therein and at least one thermoplastic resin component layer (II) at the outermost portion (2) The rubber component layer (I) is formed of an acrylic ester 50 to
A monomer mixture comprising 99.99% by mass, 49.99 to 0% by mass of another monofunctional monomer copolymerizable with the acrylate ester, and 0.01 to 10% by mass of a polyfunctional monomer (3) The thermoplastic resin component layer (II) comprises 40 to 100% by mass of a methacrylic acid ester and another monomer copolymerizable with the methacrylic acid ester. A polymer layer formed by polymerization of the monomer (ii) consisting of 60 to 0% by mass of a monomer; (4) a weight constituting the outermost layer of the thermoplastic resin component layer (II) The number average molecular weight of the coalesced particles measured by the GPC method is 30,000 or less; (5) The ratio of the total mass of the rubber component layer (I) to the total mass of the thermoplastic resin component layer (II) is as follows: (I) / 30/70 to 90/10 in layer (II) And (6) an average particle size of 150 nm or less; wherein the other components are thermoplastic resin, thermosetting resin, vulcanized rubber, glass, The present invention relates to a decorative board selected from metal, plaster, concrete, wood, particle board, and paper.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The multilayer polymer particles used in the present invention have at least one rubber component layer (I) inside and at least the thermoplastic resin component layer (II) as the outermost layer. The number of layers constituting the multilayer polymer particles used in the present invention may be at least two layers, and may be four even if three layers are formed.
It may be composed of layers or more. In the case of a two-layer structure, it has a layer (I) (center layer) / layer (II) (outermost layer) structure, and in the case of a three-layer structure, layer (I) (innermost layer) / layer (I)
(Intermediate layer) / layer (II) (outermost layer), layer (I) (innermost layer) / layer (II) (intermediate layer) / layer (II) (outermost layer) or layer (II) (innermost layer) / Layer (I) (intermediate layer) / layer (I
I) (outermost layer). In the case of a four-layer structure, for example, layer (I) (innermost layer) / layer (II) (intermediate layer) / layer (I) (intermediate layer) / layer ( II) (outermost layer). Among them, layer (I) (center layer) / layer (II) (outermost layer) in terms of excellent handleability.
Or layer (I) (innermost layer) / layer (I) (intermediate layer) / layer (II) (outermost layer) or layer (II) (innermost layer) / layer (I) (intermediate layer) / Layer (II) (outermost layer) 3
A layer structure is preferred.

The rubber component layer (I) constituting the multilayer polymer particles used in the present invention imparts flexibility to the layer comprising the multilayer polymer particles constituting the decorative board of the present invention.

The thermoplastic resin component layer (II) constituting the multilayer polymer particles used in the present invention is different from the layer comprising the multilayer polymer particles constituting the decorative board of the present invention in weather resistance, heat resistance and heat resistance. Provides scratch resistance. Further, by imparting appropriate fluidity to the multilayer structure polymer particles, the melt kneading property and the moldability in processing into a layer (film or sheet) are improved.

The multilayer polymer particles used in the present invention are characterized by a rubber component layer (I) and a thermoplastic resin component layer (II).
By changing the composition of the above, it is possible to freely change the physical properties and moldability of the layer comprising the multilayer polymer particles constituting the decorative board of the present invention. For example,
When the proportion of the rubber component layer (I) increases, a decorative board having more excellent flexibility can be obtained. On the other hand, when the amount of the thermoplastic resin component layer (II) increases, the fluidity improves, and the moldability during molding processing improves. That is, the polymer particles having a multilayer structure used in the present invention have an extremely high degree of freedom in material design according to the application, and are excellent in flexibility themselves without requiring a complicated vulcanizing step such as a vulcanized rubber. ing.

The total mass ratio of the layer (I) to the layer (II) is
(I) / (II) needs to be in the range of 30/70 to 90/10. If the proportion of the layer (I) is smaller than this range, the elastic recovery of a molded article obtained by molding the multilayer polymer particles becomes insufficient, which is not preferable. On the other hand, if the proportion of the layer (I) is larger than this range, it is difficult to form the layer structure in a perfect form, and the melt fluidity is extremely reduced, so that kneading becomes difficult. The total mass of the layer (I) refers to the layer (I) in the multilayer polymer particles.
Is the mass of the layer when only one layer is formed,
In the case of more than layers, it is the sum of the masses of those layers. Similarly, the total mass of the layer (II) is the mass of the layer (II) when the layer (II) in the multilayer polymer particle is only one layer, and when the layer (II) is two or more layers, Is the sum of the masses of those layers. The total mass ratio of the layer (I) and the layer (II) is (I) /
In (II), it is preferably in the range of 50/50 to 90/10, and more preferably in the range of 60/40 to 80/20.

The layer (I) in the multilayer polymer particles used in the present invention is composed of an acrylate ester of 50 to 99.99.
By weight, preferably 55 to 99.9% by weight, 49.9 other monofunctional monomer copolymerizable with the acrylate ester
A monomer mixture (i) containing 9 to 0% by weight, preferably 44.9% to 0% by weight and 0.01 to 10% by weight, preferably 0.1 to 2% by weight of a polyfunctional monomer; Is a polymer layer having rubber elasticity formed by copolymerization of

Specific examples of the acrylate used to form the layer (I) include methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, s-butyl acrylate, t
Esters of acrylic acids and aliphatic alcohols such as butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate and octadecyl acrylate, for example esters of C ₁ -C ₁₈ saturated aliphatic alcohols ; esters of cycloaliphatic alcohols acrylic acid with C ₅ or C _6, such as cyclohexyl acrylate;
Esters of acrylic acid such as phenyl acrylate and phenols; esters of acrylic acid such as benzyl acrylate and aromatic alcohol; The acrylate ester may be a layer (I) (when the multilayer polymer particles have two or more layers (I), each layer (I))
Is used alone or in combination of two or more kinds in the range of 50 to 99.99% by mass based on the monomer mixture (i) used to form If the amount of the acrylate is less than 50% by mass, the rubber elasticity of the multilayer polymer particles will decrease, and if it exceeds 99.99% by mass, the structure of the multilayer polymer particles will not be formed. Neither is preferred.

The polyfunctional monomer used for forming the layer (I) is a monomer having two or more carbon-carbon double bonds in the molecule, for example, acrylic acid, methacrylic acid, Esters of unsaturated monocarboxylic acids such as cinnamic acid with unsaturated alcohols such as allyl alcohol and methallyl alcohol; diesters of the aforementioned unsaturated monocarboxylic acids with glycols such as ethylene glycol, butanediol and hexanediol; phthalic acid , Terephthalic acid, isophthalic acid, esters of dicarboxylic acids such as maleic acid and the unsaturated alcohols and the like, specifically, allyl acrylate, methallyl acrylate, allyl methacrylate,
Methallyl methacrylate, allyl cinnamate, methallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (Meth) acrylate and the like. Among these polyfunctional monomers, allyl methacrylate is particularly preferred. In addition, the above-mentioned “di (meth) acrylate” is a general term for “diacrylate” and “dimethacrylate”. The polyfunctional monomer is a monomer mixture used to form the layer (I) (or each layer (I) when the multilayer polymer particle has two or more layers (I)). In the range of 0.01 to 10% by mass with respect to (i),
They are used alone or in combination of two or more. If the amount of the polyfunctional monomer is more than 10% by mass, the polymer particles having a multilayer structure do not exhibit rubber elasticity, and the elastic recovery becomes insufficient, which is not preferable. When the amount of the polyfunctional monomer is less than 0.01% by mass, the layer (I) is not formed as a particle structure, which is not preferable.

In order to form the layer (I), other monofunctional monomers copolymerizable with the acrylate ester can be used in addition to the acrylate ester and the polyfunctional monomer. Examples of the other monofunctional monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate. Esters of methacrylic acids such as myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate and aliphatic alcohols, for example, esters of C _{1 to} C ₂₂ saturated aliphatic alcohols; methacrylic acid such as cyclohexyl methacrylate and C ₅ or Esters of C ₆ alicyclic alcohols; esters of methacrylic acids such as phenyl methacrylate and phenols; Methacrylic acid esters such as esters of methacrylic acid such as benzyl methacrylate and aromatic alcohols are typical, but styrene, α-methylstyrene, 1-vinylnaphthalene,
Methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-
Aromatic vinyl monomers such as 4-benzylstyrene, 4- (phenylbutyl) styrene and halogenated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; butadiene, isoprene and 2,3-dimethyl Butadiene, 2-methyl-3-ethylbutadiene,
1,3-pentadiene, 3-methyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 3,
4-dimethyl-1,3-hexadiene, 1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-
Examples include conjugated diene monomers such as octadiene, cyclopentadiene, chloroprene, and myrcene. These monomers are used, if necessary, to form a layer (I) (when the multilayered polymer particle has two or more layers (I), each layer (I)). At a rate of 49.99% by mass or less based on the monomer mixture (i),
They can be used alone or in combination of two or more. When the proportion of the other monofunctional monomer exceeds 49.99% by mass, the weather resistance of the multilayer polymer particles becomes insufficient, which is not preferable.

The layer (II) in the multilayer polymer particles used in the present invention is composed of methacrylic acid ester 40 to 100.
% By mass, preferably 60 to 99% by mass, more preferably 80 to 99% by mass, and 60 to 0% by mass, preferably 40 to 1% by mass, and more preferably 20 to 1% by mass of other monomers copolymerizable therewith. It is a polymer layer having thermoplasticity formed by polymerization of the monomer (ii) consisting of mass%. When the amount of the methacrylic acid ester is less than 40% by mass, the weather resistance of the multilayer polymer particles becomes insufficient.

Specific examples of the methacrylate used for forming the layer (II) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, and hexyl methacrylate. Octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl methacrylate, palmityl methacrylate,
Stearyl methacrylate, behenyl methacrylate,
Octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like can be mentioned, and methyl methacrylate is preferable.

Specific examples of other copolymerizable monomers used for forming the layer (II) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate and isobutyl acrylate. , S-butyl acrylate, t-butyl acrylate, pentyl acrylate,
Esters of acrylic acid such as hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate and octadecyl acrylate with aliphatic alcohols, for example, esters with C ₁ -C ₁₈ saturated aliphatic alcohols; acrylic acid such as cyclohexyl acrylate C esters of alicyclic alcohols ₅ or C _6; styrene, alpha-methyl styrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propyl styrene, 4
-Cyclohexylstyrene, 4-dodecylstyrene, 2
Aromatic vinyl monomers such as -ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and halogenated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; maleimide, N-methylmaleimide Maleimide monomers such as N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide; Examples include the polyfunctional monomers shown in the above examples. Among these, alkyl acrylates such as methyl acrylate, ethyl acrylate and n-butyl acrylate are preferred.

In the multilayer polymer particles used in the present invention, the number average molecular weight of the copolymer constituting at least the outermost layer of the layer (II) contained therein is G.
It is important that it is not more than 30,000 based on the measurement by the PC (gel permeation chromatography) method. If the number average molecular weight exceeds 30,000, the elasticity of the molded article obtained by molding the multilayer polymer particles becomes insufficient, and the melt fluidity may be reduced. Although the lower limit of the number average molecular weight is not necessarily strictly limited, it is preferable that the number average molecular weight does not fall below 1,000 from the viewpoint of the permeability of the multilayer polymer particles in the production process. From the viewpoint of compatibility between elastic recovery and permeability in the production process, the number-average molecular weight is 3,000 to 2
It is particularly preferred to be within the range of 000.

The average particle size of the multilayer polymer particles used in the present invention is 150 nm or less. If it is larger than 150 nm, the elastic recovery becomes insufficient. The lower limit of the average particle diameter is not particularly limited, but from the viewpoint of easily forming a predetermined layer structure of the multilayer polymer particles,
The average particle size is preferably 30 nm or more. More preferably, the average particle size is from 80 to 120 nm.

The layer comprising the polymer particles having a multilayer structure, which constitutes the decorative board of the present invention, usually has good transparency when the thickness thereof is a normal thickness as a surface layer constituting the decorative board. By adjusting the type and proportion of the monomer so that the refractive index of each polymer constituting the layer (I) and the layer (II) is close to each other, the transparency of the polymer is improved. Can be further improved.

The multi-layer polymer particles used in the present invention have a rubber component layer (I) in view of physical properties and production simplicity.
Is composed of a layer (Ia) and a layer (Ib), has a rubber component layer (Ia) at the innermost portion, and has a rubber component layer (Ib) at an adjacent portion located so as to cover the outermost surface of the innermost portion. Further, it is preferably a multilayer polymer particle having a three-layer structure having a thermoplastic resin component layer (II) on the outermost side.

The layer (Ia) in the above-mentioned preferred multilayer polymer particles comprises 50 to 99.99% by mass, preferably 55 to 99.9% by mass of an acrylate ester. Monofunctional monomer 49.99
0 to 0% by weight, preferably 44.9 to 0% by weight, and 0.01 to 10% by weight, preferably 0.1 to 2% by weight of the polyfunctional monomer.
It is a polymer layer having rubber elasticity formed by copolymerization of a monomer mixture (ia) consisting of 100% by mass. Further, the layer (Ib) is composed of 50 to 99.99% by mass, preferably 55 to 99.9% by mass of an acrylate, and 49.99 to 99.9% by mass of another monofunctional monomer copolymerizable with the acrylate.
By copolymerization of a monomer mixture (ib) consisting of 0% by weight, preferably 44.9-0% by weight, and 0.01-10% by weight, preferably 0.1-2% by weight, of a polyfunctional monomer. It is a formed polymer layer having rubber elasticity. Layer (Ia)
For forming the layer (Ib), the monomers used for forming the layer (I) described above can be used.

In a multilayer polymer particle having a three-layer structure, which is a preferred layer structure, the rubber component layers (Ia) and (Ib)
The ratio of the sum of the masses of the thermoplastic resin component layers (II) to the mass of the thermoplastic resin component layer (II) is 30 in [(Ia) + (Ib)] / (II).
/ 70 to 90/10.
When the proportion of the sum of the masses of the layer (Ia) and the layer (Ib) is smaller than this range, the elastic recovery and the flexibility become insufficient, while the proportion of the sum of the masses of the layer (Ia) and the layer (Ib) becomes smaller. If it is larger than the range, it is difficult to form the layer structure in a perfect form, and the melt fluidity is extremely reduced, so that kneading at the time of molding becomes difficult. For the purpose of making the effect of the present invention more remarkable, the ratio of the sum of the masses of the rubber component layers (Ia) and (Ib) to the mass of the thermoplastic resin component layer (II) is
In [(Ia) + (Ib)] / (II), 50/5
It is preferably in the range of 0 to 90/10,
More preferably, it is in the range of 40 to 80/20.

The ratio of the mass of the rubber component layer (Ia) to the mass of the rubber component layer (Ib) is preferably (Ia) / (Ib) in the range of 5/95 to 95/5, More preferably, it is in the range of 20/80 to 80/20. Mass of rubber component layer (Ia) and rubber component layer (Ia)
When the ratio to the mass of b) is in the range of 5/95 to 95/5, it is generally possible to achieve both good flexibility and other mechanical properties.

In order to achieve both good flexibility and other mechanical properties, the monomer mixture (ia)
Between the content (% by mass) of the acrylate in (b) and the content (% by mass) of the acrylate in the monomer mixture (ib) [(ib) (unit:% by mass) − (i
a) (unit: mass%) or (ia) (unit: mass%)
(Ib) (unit: mass%)] is generally a value of 3 mass% or more, and preferably a value in the range of 4 to 30 mass%.

The multi-layered polymer particles used in the present invention are prepared by a polymerization reaction step for forming the rubber component layer (I) and a polymerization reaction step for forming the thermoplastic resin component layer (II). By performing in order, by sequentially forming a layer from the center toward the outside, having at least one rubber component layer inside, and having at least one thermoplastic resin component layer at least the outermost, It can be produced according to a known production method for producing multi-layer polymer particles composed of two or more layers. However, it is necessary to pay attention to the following points.

(1) In the polymerization reaction step (a) for forming the rubber component layer (I), the acrylate 5
0 to 99.99% by mass, 49.99 to 0% by mass of another monofunctional monomer copolymerizable with the acrylic acid ester and 0.01 to 10% by mass of a polyfunctional monomer Copolymerizing the body mixture (i). (2) In the polymerization reaction step (b) for forming the thermoplastic resin component layer (II), methacrylic acid ester 4
A monomer (ii) comprising 0 to 100% by mass and 60 to 0% by mass of another monomer copolymerizable with the methacrylic acid ester;
To polymerize.

(3) In the polymerization reaction step (b), at least in the polymerization reaction step for forming the outermost thermoplastic resin component layer (II), a molecular weight modifier is added to the monomer (ii). The polymerization reaction is performed at a ratio of 0.4 to 10% by mass. (4) The ratio of the total mass of the monomer mixture (i) to the total mass of the monomer (ii) used in the whole polymerization reaction step is calculated as follows: monomer mixture (i) / monomer (ii) 30/70 to 90/10
Within the range. (5) The average particle size of the multilayer polymer particles at the time when all the polymerization reaction steps have been completed is controlled to be 150 nm or less.

The polymerization method for producing the multi-layered polymer particles used in the present invention is not particularly limited. For example, emulsification may be carried out according to a known polymerization method for producing ordinary multi-layered polymer particles. A polymerization method, a suspension polymerization method, a solution polymerization method, or a combination thereof can be employed.

For example, in emulsion polymerization, according to known means,
By performing polymerization for forming each layer, the multilayer polymer particles of the present invention can be obtained. The temperature of the emulsion polymerization is not necessarily limited, but a general range is from 0 to 100C. As the emulsifier used here,
Alkali metal salts of fatty acids such as sodium oleate, sodium laurate and sodium stearate; sulfates of fatty alcohols such as sodium lauryl sulfate; rosinates such as potassium rosinate; alkylaryl sulfonic acids such as dodecylbenzenesulfonic acid And the like, and these are used in one kind or in combination of two or more kinds. Since the average particle size of the multilayer structure polymer particles obtained by emulsion polymerization is affected by polymerization conditions such as the amount of the emulsifier added, by appropriately selecting those conditions, the final multilayer structure polymer particles can be easily obtained. The average particle size can be controlled to 150 nm or less.

As the polymerization initiator used in the emulsion polymerization,
Radical polymerization initiators are common. As specific examples of the radical polymerization initiator, peroxides such as persulfate, azobisisobutyronitrile, and benzoyl peroxide can be used alone. Further, as a radical polymerization initiator, cumene hydroperoxide, diisopropylbenzene hydroperoxide, organic hydroperoxides such as paramenthane hydroperoxide,
A redox initiator in combination with a reducing agent such as a transition metal salt can also be used.

As described above, a predetermined amount of a predetermined monomer mixture is sequentially polymerized in accordance with a known emulsion polymerization method, whereby a predetermined polymer layer is formed stepwise from the center of the particles to the outside. However, in order to produce the multilayer polymer particles used in the present invention, in the polymerization reaction step for forming at least the outermost layer, a molecular weight modifier is used as a monomer (ii) It is particularly important to use the compound in an amount in the range of from 0.4 to 10% by mass with respect to the amount of). When producing ordinary multi-layer polymer particles, the amount of the molecular weight regulator used in the polymerization reaction for forming the outermost thermoplastic resin component layer is generally from 0 to 0. Although it is about 3% by mass, when the amount is less than 0.4% by mass, the number average molecular weight of the thermoplastic resin component constituting the layer becomes too high, and the multilayer structure polymer particles constituting the decorative board are formed. In some cases, the flexibility of the layer made of the resin becomes insufficient, and the fluidity of the molding becomes insufficient. For the purpose of the present invention, it is sufficient that the amount of the molecular weight regulator is at most 10% by mass based on the above-mentioned standard, and even if an amount larger than that is used, there is no longer any improvement in the effect of imparting flexibility. It is not desirable because the amount of the molecular weight regulator remaining in the structural polymer particles increases. The molecular weight regulator is 0.4 to 5 based on the monomer (ii).
%, More preferably in a range of 0.6 to 2% by mass.

Specific examples of the molecular weight regulator include, for example, n
-Octyl mercaptan, t-octyl mercaptan,
mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, and mercaptoethanol; terpene mixtures of terpinolene, dipentene, t-terpinene and a small amount of other cyclic terpenes; halogenated hydrocarbons such as chloroform and carbon tetrachloride; No. Of these, alkyl mercaptans such as n-octyl mercaptan are preferred.

After the emulsion polymerization, the obtained multi-layered polymer particles can be separated and obtained from the polymerization reaction system according to a known method, for example, an acid precipitation method, a salt precipitation method, a spray drying method, and a freeze coagulation method. Etc. can be adopted.

The polymer particles having a multilayer structure used in the present invention include:
A layer composed of the multi-layered polymer particles alone can be constituted, but the layer further includes polymethyl methacrylate, methyl methacrylate-styrene copolymer, other acrylic multi-layered polymer particles such as multi-layered polymer particles. By blending one or more resins, the hardness of the layer can be adjusted. In order to adjust the hardness while taking advantage of the original excellent elastic recovery property of the multilayer polymer particles used in the present invention, moderate flexibility and other good mechanical physical properties, and transparency, the multilayer polymer particles and The mass ratio of the other acrylic resin is 50/50 to 95/5, preferably 60/40 to multilayer polymer particles / other acrylic resin.
It is desirable to be within the range of 95/5.

The layer composed of the polymer particles having a multilayer structure used in the present invention may have a composition comprising the polymer particles or a composition comprising the polymer particles and another acrylic resin or a layer formed by molding them. One or more of the physical property improvers may be blended, if desired, within a range that does not impair the effects of the present invention. Such physical property improvers are not particularly limited, and include, for example, droplets, anti-fogging agents, lubricants, antioxidants, light stabilizers, coloring agents, antistatic agents, flame retardants, deodorants,
Examples include antimicrobial agents, fillers (fiber reinforcing agents such as glass fibers, inorganic fillers, etc.).

The above-mentioned compounding method is, for example, that the multi-layered polymer particles used in the present invention and other acrylic resins and / or additives used as required are mixed with the multi-layered polymer particles and other acrylic resin. It can be carried out by sufficiently mixing the resin under melt-kneading conditions.

Hereinafter, the structure of the decorative board of the present invention will be described with reference to the drawings, but the structure of the decorative board of the present invention is not limited thereto. FIG. 1 is a cross-sectional view of a decorative board having a two-layer structure composed of a layer (a) composed of multilayer polymer particles and a substrate (b) used in the present invention. FIG. 2 is a cross-sectional view of a three-layer decorative board composed of a layer (a) composed of multilayer polymer particles, a substrate (b), and an intermediate layer (c) used in the present invention.

The layer (sheet or film) comprising the multi-layered polymer particles used in the present invention constituting the a layer
Can be obtained by using an ordinary molding method such as an inflation method, a T-die method, and a calendar method. The thickness of the layer a is not particularly limited, but is preferably from 0.3 to 2 mm, and more preferably from 0.5 to 1 mm, because it is excellent in handling during roll bonding in the laminating step. For the purpose of improving the design, it is also possible to add a commercially available pattern material to form a marble or woodgrain when forming the a layer, or to emboss or print the a layer.

It should be noted that, regarding the decorative plate of the present invention, "excellent in transparency" refers to the transparency of the layer a.
The layer is generally excellent in transparency, meaning that the pattern of the base layer b and the printing or coating applied thereto can be clearly seen through the a layer, and that the color development is excellent. The layer a is generally colorless and transparent, which means that the coloring applied to the layer b can be clearly seen through the layer a as the same color.

As the base material constituting the layer b, thermoplastic resins other than the multilayer polymer particles used in the present invention, thermosetting resins, vulcanized rubber, glass, metal, gypsum, concrete, wood, At least one selected from particle board and paper is used. For the purpose of improving the design, it is also possible to print and coat the substrate (b).
The thickness of the layer b is preferably 0.5 to 50 mm,
More preferably, it is 0.6 to 40 mm.

In the configuration shown in FIG. 1, printing is performed on the back surface of a transparent sheet composed of the polymer particles having a multilayer structure used in the present invention, a heated steel plate is disposed on the printing surface side, and pressure bonding is performed by a roll. And a two-layer decorative board obtained by integrating a multilayer structure polymer particle used in the present invention with a colored thermoplastic resin such as an ABS resin by coextrusion molding.

As shown in FIG. 2, it is possible to provide at least an intermediate layer c between the a layer and the b layer. Middle layer c
Is used for the purpose of improving the design and deepness of decorative panels, and adding a commercially available pattern material to give a marble or woodgrain, or embossing or printing to add design Alternatively, a foam can be used. Moreover, it may be inserted as a reinforcing material for a decorative board. The middle layer is used for
It is also possible to provide two or more layers according to the purpose. The material of the intermediate layer is not particularly limited, and the same material as the a layer or the b layer can be used. As an example, a transparent sheet composed of the multilayer structure polymer particles of the present invention and a polyester film subjected to woodgrain printing are stacked in two layers, and a heated steel sheet is arranged on the woodgrain printed film side, and pressed with a roll. And an integrated decorative board. The thickness of the c layer is
It is preferably 0.01 to 2 mm, and 0.02 to 1 m
m is more preferable.

Specific examples of other thermoplastic resins capable of forming a layer composed of other components in the present invention include polyethylene, polypropylene, polybutene-1, and poly-4-.
Polyolefin resins such as methylpentene-1 and polynorbornene; ethylene ionomers; polystyrene;
Styrene-maleic anhydride copolymer, high impact polystyrene, ABS, AES, AAS, ACS, MBS
Acrylic resins such as polymethyl methacrylate, methyl methacrylate-styrene copolymer, and other acrylic multi-layer polymer particles different from the multi-layer polymer particles used in the present invention; polyethylene terephthalate, polybutylene Polyester resins such as terephthalate; polyamide resins such as nylon 6 and nylon 66;
Polycarbonate and the like.

Specific examples of the thermosetting resin which can form a layer composed of other components in the present invention include epoxy resin, unsaturated polyester, phenol resin, urea resin, melamine resin and the like. Specific examples of metals that can form a layer composed of other components in the present invention include iron, aluminum, copper, brass, tin, zinc and alloys containing them, and these are applied in the form of a sheet. Is done. In the present invention, paper that can constitute a layer composed of other components includes, in addition to materials generally called paper, cellophane, parchment paper (sulfuric paper), flame-retardant paper,
Nonwoven fabrics, glass fibers and the like can be used. The decorative board of the present invention can be preferably used as a wallpaper when a flexible substrate such as the above-mentioned paper, vulcanized rubber, or flexible thermoplastic resin is used.

The method of bonding each layer of the decorative board of the present invention is as follows.
There is no particular limitation, and a known technique such as a method using heat fusion such as hot pressing or heat lamination, or a dry lamination method using an adhesive can be used. When using a thermoplastic resin, two or more layers can be integrated by coextrusion.

Further, an adhesive can be used for the purpose of strengthening each lamination interface, and in this case, a decorative plate having substantially three or more layers is obtained. Urethane-based adhesive,
Commercially available adhesives such as acrylic and epoxy can be used. It is also possible to add a pattern material to the adhesive to impart adhesiveness and design. When an adhesive is used, an existing adhesive such as a urethane-based, acrylic-based, or epoxy-based adhesive can be freely selected depending on a material to be combined, and can be integrated by a known technique. Further, for the purpose of improving the adhesiveness, the primer may be applied and then adhered via an adhesive.

The decorative plate of the present invention is used as decorative steel plate, wallpaper, other decorative plate, etc. used for ceiling materials, wall materials, floor materials, etc. of hospitals, restaurants, offices, factories, vehicles, general households and the like. be able to.

[0049]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, each measured value in an Example followed the following evaluation method. The average particle diameter of the multilayer polymer particles was measured by a dynamic light scattering method using a laser particle size analyzer PAR-III (manufactured by Otsuka Electronics Co., Ltd.) using a sample collected from the latex after completion of the polymerization. Analyzed by the method.

The number average molecular weight of the polymer component constituting the outermost layer of the multilayer polymer particles was obtained by sufficiently stirring a sample of the multilayer polymer particles in toluene at room temperature and then centrifuging the sample. The solution was measured by the GPC method, and the obtained value was regarded as the number average molecular weight of the polymer constituting the outermost layer in the present invention. The hardness of the sheet was measured using a type A hardness meter (manufactured by Oscar) according to JIS K6301.
It measured according to. The weather resistance was measured using a sunshine weather meter S80 manufactured by Suga Test Machine under the conditions of a black panel temperature of 63 ° C., a humidity of 50%, and a spray cycle of 18 minutes / 2 hours. The later yellowing degree (b value) was measured.

Production Example of Multilayered Polymer Particles Under a nitrogen atmosphere, a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel was charged with 2800 parts by mass of distilled water, 8.4 parts by mass of sodium dodecylbenzenesulfonate as an emulsifier, 1.7 parts by mass of sodium carbonate was added, and the mixture was heated to 80 ° C. and uniformly dissolved. Next, at the same temperature, after adding 0.7 parts by mass of potassium peroxodisulfate, 420 parts by mass of n-butyl acrylate and 198 methyl methacrylate were added.
A mixture consisting of parts by mass, 82 parts by mass of styrene, 2.8 parts by mass of allyl methacrylate, and 3.5 parts by mass of sodium polyoxyethylene alkylphosphate was dropped from a dropping funnel over 60 minutes to form a first layer. After dropping,
The reaction was continued at 80 ° C. for another 1 hour, and it was confirmed by gas chromatography that 99% or more of each monomer was consumed. Next, 0.35 parts by mass of potassium peroxodisulfate was added to the obtained copolymer latex, and then 280 parts by mass of n-butyl acrylate and 14 parts of methyl methacrylate 14 were added.
A mixture consisting of parts by mass, 56 parts by mass of styrene, 1.4 parts by mass of allyl methacrylate and 1.8 parts by mass of sodium polyoxyethylene alkyl phosphate was dropped from the dropping funnel over 30 minutes to form a second layer. After dropping,
The reaction was continued at 80 ° C. for another 1 hour, and it was confirmed by gas chromatography that 99% or more of the monomer was consumed.

Next, after adding 0.35 parts by mass of potassium peroxodisulfate to the obtained copolymer latex, 334 parts by mass of methyl methacrylate, 18 parts by mass of methyl acrylate, 3.5 parts by mass of n-octyl mercaptan and Sodium oxyethylene alkyl phosphate 1.8
A part by mass was dropped from the dropping funnel over 30 minutes to form a third layer. After completion of the dropwise addition, the reaction was further continued at 80 ° C. for 1 hour, and it was confirmed by gas chromatography that 99.9% or more of the monomer was consumed, and the polymerization was terminated. The average particle diameter of the particles in the obtained latex was 100 nm. This latex was cooled to −30 ° C. for 24 hours to freeze-aggregate, and then the aggregate was thawed and taken out. 50 ℃
And dried under reduced pressure for 2 days to obtain three-layer type polymer particles [A] in the form of aggregated powder. Table 1 shows the physical property values of the multilayer polymer particles [A].

[0053]

[Table 1]

Example 1 Multilayer polymer particles [A] were extruded at a rate of 20 kg / hr from a single-screw extruder having a diameter of 40 mm, led to a die for manufacturing a sheet having a width of 200 mm, and the sheet-like molten resin discharged from the die was completely discharged. The sheet was cooled and mirror-finished by passing through a polishing roll adjusted to a thickness of 0.5 mm to obtain a target sheet. The JISA hardness of the obtained sheet was 70. The obtained multilayer structure polymer particles [A] sheet was coated with a polyurethane resin-based adhesive by a roll coater and heated to about 200 ° C., into a 0.8 mm thick cold-rolled steel sheet type steel sheet, A decorative steel plate having two layers was obtained by pressing with a roll so that the adhesive-coated surface and the steel plate overlapped each other. Table 2 shows the results of the accelerated exposure test for this decorative steel sheet.

Example 2 A mixture of 80 parts by mass of the polymer particles [A] having a multilayer structure and 20 parts by mass of a hard acrylic resin, Parapet G (manufactured by Kuraray Co., Ltd.) was supplied from a single-screw extruder having a diameter of 40 mm at a pressure of 20 kg / hr. Extruded at a rate and led to a 200 mm wide sheet manufacturing die,
The total thickness of the sheet-like molten resin discharged from the die is 1.0 m
The sheet was cooled and mirror-finished by passing through a polishing roll adjusted to have a thickness of m, thereby obtaining a target sheet. JIS of the obtained sheet
The A hardness was 90. The resulting sheet is coated with a polyurethane resin adhesive by a roll coater,
0.8 of cold thick-rolled steel sheet type heated to about 00 ° C
A two-layer decorative steel sheet was obtained by pressing the steel sheet having a thickness of 2 mm with a roll so that the adhesive-coated surface and the steel sheet overlapped each other. Table 2 shows the results of the accelerated exposure test for this decorative steel sheet.

Comparative Example 1 Vinica Compound CE65GC as a vinyl chloride resin
(Mitsubishi Chemical MKV Co., Ltd.) was extruded from a φ40 mm single screw extruder at a rate of 20 kg / hr, led to a 200 mm wide sheet manufacturing die, and the sheet-like molten resin discharged from the die was 1.0 mm thick. Then, the sheet was cooled and mirror-finished by passing through a polishing roll adjusted to obtain a target sheet.
The JISA hardness of the obtained sheet was 65. The obtained sheet was coated with a polyurethane resin-based adhesive by a roll coater and heated to about 200 ° C., on a 0.8 mm thick cold-rolled steel sheet type steel sheet, the adhesive-coated surface and the steel sheet were combined. A decorative steel plate consisting of two layers was obtained by pressing with a roll so as to overlap. Table 2 shows the results of the accelerated exposure test for this decorative steel sheet.

[0057]

[Table 2]

Example 3 The sheet produced in Example 1 was subjected to woodgrain printing.
Except that a film made of polyethylene terephthalate having a thickness of 0 μm was laminated as an intermediate layer, the same process as in Example 1 was performed.
A woodgrain veneer with a soft texture was obtained. Example 4 The sheet produced in Example 1 was subjected to woodgrain printing, an adhesive was applied to the printed surface in the same manner as in Example 1, and pressed on a 1 cm thick particle board in the same manner as in Example 1. A decorative panel with excellent soft texture was obtained.

[0059]

According to the present invention, the decorative board of the present invention which is obtained by laminating a layer composed of specific polymer particles having a multilayer structure and a layer composed of other components (resin, rubber, metal, paper, etc.) has a specific multilayer structure. The layer made of polymer particles is a soft resin that has almost the same flexibility as vinyl chloride resin, but also has the weather resistance characteristic of acrylic resin, so it can be used outdoors, which was not possible before. become. Furthermore, since the specific multi-layered polymer particles have almost the same moldability as conventional vinyl chloride resin, the conventional production equipment for vinyl chloride resin can be used as it is, and no additional capital investment is required. Also has.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a decorative board having a two-layer structure composed of a layer (a) composed of polymer particles having a multilayer structure and a substrate (b) used in the present invention.

FIG. 2 is a cross-sectional view of a three-layer decorative board composed of a layer (a) composed of polymer particles having a multilayer structure, a substrate (b), and an intermediate layer (c) used in the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Yamashita 41, Miyukigaoka, Tsukuba, Ibaraki Pref., Kuraray Co., Ltd. ) Inventor Tatsuya Naruse 2-28 Kurashiki-cho, Nakajo-machi, Kitakanbara-gun, Niigata F-term in Kuraray Co., Ltd. 4F100 AB01B AE02B AE06B AG00B AK01A AK01B AK25A AK51G AL01A AL05A AN00B AN02A AP01B AP03B BA02 CB00 DD32A DE01A GB07 GB31 JB13B JB16A JB16B JK13 JK17 JL09 JL10 JM01YN01

Claims (3)

[Claims] 1. A decorative board comprising at least one layer composed of multilayer polymer particles and at least one layer composed of other components laminated on each other, wherein said multilayer polymer particles are (1) A) multilayer polymer particles comprising at least one rubber component layer (I) therein and at least one thermoplastic resin component layer (II) at least outermost, comprising two or more layers; (2) The rubber component layer (I) is made of an acrylate ester 50-
A monomer mixture comprising 99.99% by mass, 49.99 to 0% by mass of another monofunctional monomer copolymerizable with the acrylate ester, and 0.01 to 10% by mass of a polyfunctional monomer (3) The thermoplastic resin component layer (II) comprises 40 to 100% by mass of a methacrylic acid ester and another monomer copolymerizable with the methacrylic acid ester. A polymer layer formed by polymerization of the monomer (ii) consisting of 60 to 0% by mass of a monomer; (4) a weight constituting the outermost layer of the thermoplastic resin component layer (II) The number average molecular weight of the coalesced particles measured by the GPC method is 30,000 or less; (5) The ratio of the total mass of the rubber component layer (I) to the total mass of the thermoplastic resin component layer (II) is as follows: (I) / 30/70 to 90/10 in layer (II) And (6) an average particle diameter of 150 nm or less; wherein the other component is another thermoplastic resin, a thermosetting resin, or a vulcanized rubber. A decorative board selected from glass, metal, plaster, concrete, wood, particle board and paper. 2. The decorative plate according to claim 1, which is a decorative steel plate. 3. The layer comprising the polymer particles having a multilayer structure contains another acrylic resin and / or a property improving agent.
Or the decorative plate according to 2.