JPH05138838A - Laminate - Google Patents

Abstract

PURPOSE:To obtain a laminate of thermosetting resin with good weatherability and impact resistance capable of being used outdoors. CONSTITUTION:On at least one surface of a thermosetting resin sheet, an acrylic resin is laminated which has a multi-layered structure comprising an innermost layered polymer, cross-linking elastic layered polymer, outermost layered polymer and intermediate layered polymer (D), and also has a content of at least 50% gel and a content of 500ppm or less residual metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate of thermosetting resin such as melamine resin and phenol resin having excellent weather resistance and impact resistance.

[0002]

2. Description of the Related Art Melamine resins and phenolic resins are used as inner wall materials, floor materials, etc. by taking advantage of their characteristics such as surface hardness and solvent resistance. However, they have poor weather resistance and cause problems of discoloration and deterioration due to long-term use. There is. On the other hand, the acrylic resin can suppress deterioration of the weather resistance of the base material by adhering or laminating due to its good weather resistance.
The weather resistance of the base material is obtained by laminating an acrylic resin film containing methyl methacrylate as a main component and made of a multilayer structure polymer having a taper structure as described in JP-A-129449 and JP-A-52-56150. It not only suppresses deterioration, but also has excellent impact resistance, water whitening resistance, solvent resistance, stress whitening resistance, and also has the function of giving design properties to the base material, but thermosetting like melamine resin and phenol resin There is a problem in that the adhesiveness with the resin is poor and a sufficient adhesive force cannot be obtained by thermal bonding.

[0003]

The object of the present invention is to provide excellent weather resistance, impact resistance, solvent resistance, water whitening resistance, stress whitening resistance, and thermosetting property of melamine resin, phenol resin and the like. It is to provide a resin laminate.

[0004]

The gist of the present invention lies in the following innermost layer polymer (A), crosslinked elastic layer polymer (B), outermost layer polymer (C) and intermediate layer polymer (D). )
And a gel content of at least 50% and a residual metal content of 500 ppm or less, the acrylic resin composition having a multilayer structure polymer is laminated on at least one surface of a thermosetting resin plate. Innermost layer polymer (A) 80 to 100 parts by weight of alkyl acrylate having an alkyl group of 1 to 8 carbon atoms and / or alkyl methacrylate (A ₁ ) having an alkyl group of 1 to 4 carbon atoms of 0 to 20 parts by weight monomers having a copolymerizable double bond (a ₂₎ a polyfunctional monomer of 0 parts by weight _{(a 3) (a 1)} 0 to 100 parts by weight of the total of ~ (a ₃₎ .1
5 parts by weight of the grafting agent obtained from the composition of (A _4), polymer crosslinked elastic layer polymer present in the core (B) alkyl acrylates having an alkyl group having 1 to 8 carbon atoms of 80 to 100 parts by weight (B ₁₎ a monomer having a copolymerizable double bond 0-20 parts by weight (B ₂₎ a polyfunctional monomer of 0 parts by weight _{(B 3) (B 1)} ~ (B 3 ) 0.1 to 100 parts by weight
Polymer present from the composition of 5 parts by weight of the graft crossing agent (B ₄ ) which is present outside the innermost layer polymer (A) Outermost layer polymer (C) 51 to 100 parts by weight of C1 to C4 Alkyl methacrylate (C ₁ ) 0.1 to 40 parts by weight of hydroxyalkyl (meth) acrylate (C ₂ ) having an alkyl group of 1 to 8 carbons 0 to 49 parts by weight of a monomer having a copolymerizable double bond obtained from the composition of the body (C _3), a polymer intermediate layer polymer present on the outer surface (D) 10 to 90 parts by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms (D ₁₎ 90 to 10 Alkyl methacrylate (D ₂ ) having 1 to 4 carbon atoms of an alkyl group 0 to 20 parts by weight of a monomer (D ₃ ) having a copolymerizable double bond 0 to 10 parts of polyfunctionality Monomer (D ₄ ) (D ₁ ) to (D ₄ ) 0.1 to 100 parts by weight
It is obtained from the composition of ₅ parts by weight of the graft crossing agent (D ₅ ), is present between the crosslinked elastic layer polymer (B) and the outermost layer polymer (C), and the amount of the alkyl acrylate (D ₁ ) is the crosslinked elastic layer. Polymer adjusted so as to monotonically decrease from the layer polymer (B) to the outermost layer polymer (C)

The acrylic resin composition of the present invention comprises a crosslinked elastic layer polymer containing alkyl acrylate as a main component in the presence of the innermost layer polymer (A) containing a specific alkyl acrylate and / or alkyl methacrylate as a main component. B) is polymerized, an outermost layer polymer (C) containing an alkyl methacrylate as a main component and a specific hydroxyl group-containing monomer component is disposed as the outermost layer, and the polymer (B) layer and the polymer (C) are disposed. An intermediate layer polymer (D) layer adjusted so that the amount of the alkyl acrylate as a monomer component monotonically decreases from the polymer (B) layer to the polymer (C) layer. It is an intervening multi-layered polymer. In addition, this multi-layer structure polymer has a gel content and a residual metal content of the final polymer composition in a specific amount by using a specific range amount of the graft crossing agent in each polymer layer other than the outermost layer polymer (C). It is stipulated.

Generally, acrylic rubbers are superior in weather resistance to diene rubbers, but on the other hand, they exhibit slow elastic recovery, large deformation under stress, and low rubber efficiency. That is, in order to have various properties such as solvent resistance and water whitening resistance while maintaining excellent weather resistance, there is a limit to the conventional elastic structure consisting of only one layer. In the present invention, the innermost layer polymer (A) is present in the core of the crosslinked elastic layer polymer (B) in order to solve such a drawback. That is, when stress is applied, the stress concentrated in the crosslinked elastic layer polymer (B) layer is dispersed and relaxed by the presence of the innermost layer polymer (A), and as a result, the occurrence rate of microvoids becomes large. Therefore, it is considered that even if no apparent stress whitening occurs, excellent impact resistance is exhibited.

The number of carbon atoms constituting the innermost layer polymer (A) is 1 to
Alkyl acrylate having 8 alkyl groups (A ₁ )
May be linear or branched and may be methyl acrylate, ethyl acrylate, propyl acrylate,
2-Ethylhexyl acrylate, n-octyl acrylate, etc. may be used alone or as a mixture, but those having a low glass transition point Tg are more preferable. Also, carbon number 1
Alkyl methacrylate (A
_{As 1} ), linear or branched may be used, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. may be used alone or in combination. Further, these alkyl acrylates and alkyl methacrylates may be mixed and used. These alkyl (meth) acrylates (A ₁ ) are 80-
It is used in the range of 100 parts by weight. Further, it is preferable that all of these alkyl (meth) acrylates (A ₁ ) are subsequently used in all the multi-stage layers (A) to (D).
In any of (A) to (D), two or more kinds of monomers may be mixed or different kinds of acrylate may be used depending on the final purpose.

A monomer having a copolymerizable double bond (A
₂ ) Examples include lower alkyl acrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic monomers such as acrylic acid and methacrylic acid, aromatic vinyl monomers such as styrene and alkyl-substituted styrene, acrylonitrile and methacrylonitrile. The cyanovinyl monomer is used in the range of 0 to 20 parts by weight.

Polyfunctional monomers (A ₃ ) include alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and propylene glycol dimethacrylate. Preferably, polyvinylbenzene such as divinylbenzene and trivinylbenzene, alkylene glycol diacrylate and the like can be used. Even if the polyfunctional monomer (A ₃ ) is not used at all, a fairly stable multilayer structure polymer can be obtained as long as the graft crossing agent (A ₄ ) is present, but when the hot strength is strictly required. Etc. are preferably added, and they are used in the range of 0 to 10 parts by weight.

The graft crossing agent (A ₄ ) is a compound having two or more unsaturated groups having an addition polymerization property and having a large difference in the polymerization reactivity of each unsaturated group, for example, a copolymerizable α. , Allyl, methallyl or crotyl esters of β-unsaturated carboxylic acids or dicarboxylic acids, preferably allyl esters of acrylic acid, methacrylic acid, maleic acid and fumaric acid are used, and allyl methacrylate is particularly effective. Other triallyl cyanurate,
Triallyl isocyanurate is also effective. These may be used alone or as a mixture. In such a graft crossing agent, mainly the conjugated unsaturated bond of the ester reacts much faster than an allyl group, a methallyl group or a crotyl group and chemically bonds. During this period, a substantial substantial amount of the allyl group, methallyl group or crotyl group works effectively during the polymerization of the crosslinked elastic layer polymer (B) of the next layer to give a graft bond between two adjacent layers.

The amount of the graft crossing agent (A ₄ ) used is extremely important and is 0.1 to 5 parts by weight, preferably 0.5, based on 100 parts by weight of the total amount of the above components (A ₁ ) to (A ₃ ). Used in the range of up to 2 parts by weight. If it is less than 0.1 part by weight, the effective amount of graft bond is small, and if it exceeds 5 parts by weight, the reaction amount with the crosslinked elastic layer polymer (B) polymerized and formed in the second stage becomes large, which is a feature of the present invention. The elasticity of the two-layer cross-linked rubber elastic body having the two-layer elastic body structure is deteriorated.

The Tg of the innermost layer polymer (A) is appropriately set according to the required physical properties of the final polymer. Further, the crosslink density thereof is generally the same as that of the crosslinked elastic layer polymer (B) or rather higher, which is advantageous in terms of quality. The innermost layer polymer (A) and the crosslinked elastic layer polymer (B) may have the same composition, but even in that case, the two-layered elastic body structure formed by two-stage polymerization is not a temporary charge. It is important that the polymer (A) is more advantageous in setting the amount of catalyst, crosslinking density and the like. Considering the initial polymerizability, the presence of the innermost layer polymer (A) is extremely important in order to obtain a stable polymer having a multi-layer structure, and it is generally preferred that the catalyst amount be the largest in each polymer layer.

The use of the graft crossing agent (A ₄ ) is effective for synthesizing a two-layer elastic body structure chemically bonded to the crosslinked elastic layer polymer (B) formed in the second stage. It is essential. Without this graft bond, the two-layer elastic structure easily undergoes phase breakage during melt formation, which not only reduces the rubber efficiency but also does not exhibit the desired excellent weather resistance, solvent resistance, water whitening resistance, etc. .. The content of the innermost layer polymer (A) in the multilayer structure polymer is 5 to 35% by weight, further 5 to
It is preferably 15% by weight, and is preferably lower than the content of the crosslinked elastic layer polymer (B).

Next, the crosslinked elastic layer polymer (B) will be described. The crosslinked elastic layer polymer (B) is a main component that imparts rubber elasticity to the multilayer structure polymer, and constitutes this (B
₁₎ - (in B ₄₎ is used in the innermost layer polymer described above (A) (A ₁₎ to (A ₄₎ is used respectively. (B ₁ )
80 to 100 parts by weight of the component, 0 to 20 parts by weight of the (B ₂ ) component, 0 to 10 parts by weight of the (B ₃ ) component, and the total amount of (B ₁ ) to (B ₃ ) of the (B ₄ ) component. 0.1 to 5 for 100 copies
It is used in the range of parts by weight, respectively. The Tg of the crosslinked elastic layer polymer (B) alone is preferably 0 ° C. or lower, and more preferably −30 ° C. or lower, to give preferable physical properties.

The content of the crosslinked elastic layer polymer (B) in the multilayer structure polymer is preferably in the range of 10 to 45% by weight,
Further, it is preferably higher than the content of the innermost layer polymer (A). In this way, the conventional single rubber has been achieved by having a two-layer crosslinked rubber elastic body having a two-layer elastic body structure in which the innermost layer polymer (A) and the crosslinked elastic layer polymer (B) are graft-polymerized. It becomes possible to satisfy various properties that could not be achieved at the same time. The two-layer crosslinked rubber elastic body had a gel content of 85% or more and a swelling degree of 3 determined by the following measuring method.
It is preferable that it is set in the range of -13 to obtain excellent solvent resistance and water whitening resistance.

(Method for measuring gel content and swelling degree) JIS K
A predetermined amount of two-layer crosslinked rubber elastic body is sampled according to -6388,
After dipping and swelling in methyl ethyl ketone (hereinafter referred to as MEK) at 25 ° C for 48 hours, the MEK attached was wiped off, the weight was measured, and then the MEK was dried in a vacuum dryer.
Is removed by drying to obtain a constant weight, and the absolute dry weight is read and calculated by the following formula. Swelling degree = (weight after MEK swelling−excess dry weight) / excess dry weight Gel content (%) = (excess dry weight / weight of collected sample)
× 100

Generally, when the degree of polymerization of the crosslinked elastic layer polymer (B) is as high as possible, high impact strength is imparted to the final polymer. On the other hand, the innermost layer polymer (A) serving as the core is not limited to this, but rather the amount of the catalyst used is large and the graft activator is also used in a large amount for the stability of intended polymerization including particle formation. The better the performance as a two-layer crosslinked rubber elastic body, the better. Such a composite effect cannot be obtained by a conventional single-layer rubber polymer system.

The outermost layer polymer (C) should contribute to the multi-layer structure polymer in terms of adhesiveness, moldability, mechanical properties, etc., and the component (A ₁ ) constitutes the component (C ₁ ) (C ₃ )
As the component, those used for the component (A ₂ ) are used. The hydroxyalkyl (meth) acrylate (C ₃ ) having an alkyl group having 1 to 8 carbon atoms may be linear or branched and may be hydroxymethyl acrylate, hydroxyethyl acrylate, 4-hydroxybutyl acrylate, hydroxymethyl. Methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. may be used alone or in combination.

In the present invention, the outermost layer polymer (C) is used in an amount of 0.1-40 parts by weight, preferably 0.5-.
The intended purpose described above can be achieved by copolymerizing 20 parts by weight of a hydroxyalkyl (meth) acrylate having 1 to 8 carbon atoms. The content of the outermost layer polymer (C) in the multilayer structure polymer is preferably 10 to 80% by weight, more preferably 40 to 60% by weight.

The multilayer structure polymer of the present invention comprises the above innermost layer polymer (A), crosslinked elastic layer polymer (B) and outermost layer polymer (C) as basic constitutional units, and further comprises a crosslinked elastic layer polymer ( The intermediate layer polymer (D) is present between the layer B) and the outermost layer polymer (C) layer. This intermediate layer polymer (D) is 10 to 9
0 parts by weight of an alkyl acrylate (D ₁ ) having an alkyl group having 1 to 8 carbon atoms, 90 to 10 parts by weight of 1 to carbon atoms
4 alkyl group-containing alkyl methacrylate (D ₂ ), 0 to 20 parts by weight of a monomer having a copolymerizable double bond (D ₃ ), 0 to 10 parts by weight of a polyfunctional monomer (D ₄ ), and the total amount of these (D ₁ ) to (D ₄ ) 10
It is composed of 0.1 to 5 parts by weight of the graft crossing agent (D ₅ ) based on 0 parts by weight. In the intermediate layer polymer (D) layer, the amount of the alkyl acrylate component in the intermediate layer polymer (D) layer monotonically decreases from the crosslinked elastic layer polymer (B) layer to the outermost layer polymer (C) layer. At least one layer is arranged so as to do so.

[0021] The herein (D ₁₎ alkyl acrylates that can be used for (A _1), can be used alkyl methacrylates that can be used for (A ₁₎ to _{(D 2), (D 3} ) ~
As each component of (D ₅ ), each component that can be used in the above (A ₂ ) to (A ₄ ) can be used. The graft crossing agent (D ₅ ) used for the intermediate layer (D) is essential for tightly binding the polymer layers and for obtaining excellent properties. Since the (B) layer and the (C) layer have different refractive indexes, the (D) layer is provided in order to make the refractive index gradient. In the layer (D), the amount of the acrylate component must always decrease monotonically, but the acrylate supply amount may be changed to control the acrylate component distribution. The content of the intermediate layer (D) in the multilayer structure polymer is preferably from 5 to 35% by weight, and when the content is less than 5% by weight, the function as an intermediate layer is insufficient, and when it exceeds 35% by weight, the balance of the final polymer is improved. It may collapse.

The multi-layer structure polymer has the above-mentioned (A), (B),
Although it is composed of the polymer layers of (C) and (D), it is necessary that the gel content is at least 50% in order to obtain further excellent solvent resistance and water whitening resistance. This is one of the major features of the present invention. In this case, the gel content is two-layer crosslinked rubber elastic body (consisting of the innermost layer polymer (A) and the crosslinked elastic layer polymer (B)) itself, the intermediate layer polymer (D) and the outermost layer polymer (C). ) And a graft component to the crosslinked rubber elastic body,
Here, the definition of the gel content is the same as above. The component is the added weight of the two-layer crosslinked rubber elastic body and the graft chain and can be replaced by the graft ratio. However, in the present invention, since the multilayer structure polymer has a special structure, the gel content has a gel content of I used it as a guide. From the viewpoint of solvent resistance, the larger the gel content is, the more advantageous it is. However, from the viewpoint of easy moldability, the presence of a free polymer is required, so that the upper limit of the gel content is preferably about 80%.

An aqueous dispersion polymerization method is suitable for producing a polymer having a multilayer structure, and the dispersed particle size of the final polymer is not particularly limited, but a structure having a most balanced range of about 800 to 2000 angstrom is obtained. Be done. In addition,
There are no particular restrictions on the surfactants, catalysts, etc. used in the production, and if necessary, additives such as antioxidants and lubricants can be added for salting out. When salting out using a metal salt, it is extremely important that the residual metal content in the final product be 500 ppm or less, which is one of the major features of the present invention. Especially when using a metal salt having a strong affinity for water such as magnesium and sodium as a salting-out agent, unless the residual metal content is reduced as much as possible, a whitening reduction occurs when the final polymer is immersed in boiling water. It becomes a big problem in practical use. In addition, calcium-based,
Sulfuric acid-based coagulation shows a relatively good tendency, but in any case, in order to give excellent water whitening resistance, it is necessary to reduce the residual metal content to 500 ppm or less by washing the polymer. Therefore, the smaller the amount of residual metal, the better. As a method for producing a multi-layer structure polymer, a sequential multi-stage polymerization method by emulsion polymerization is the most suitable polymerization method. It can also be carried out by the emulsion suspension polymerization method of conversion.

The acrylic resin composition of the present invention may be used alone, or may be further blended with a homopolymer or copolymer of an alkyl (meth) acrylate having 1 to 8 carbon atoms. is there. To bond the acrylic resin composition of the present invention to a thermosetting resin substrate such as a melamine resin or a phenol resin, a method of forming the acrylic resin composition into a film or sheet and then thermally bonding it to the substrate And a method in which the acrylic resin composition is dissolved in an appropriate organic solvent, applied on a substrate and then dried, and may be arbitrarily selected according to the purpose. When the acrylic resin composition of the present invention is used to form a film or sheet, it may be a single layer or a double layer. In the case of a double layer, the present acrylic resin composition is disposed in at least the adhesive layer with the substrate. It's fine.

[0025]

The present invention will be described in more detail with reference to the following examples. In the examples, "parts" means "parts by weight". Examples 1 to 3 (Production of acrylic resin composition) 250 parts of ion-exchanged water, 2 parts of ester soda salt of sulphosuccinic acid and 0.05 part of Rongalit (SFS) were charged in a polymerization container with a condenser and stirred under nitrogen. After methyl methacrylate (MMA)
1.6 parts, butyl acrylate (BuA) 8 parts, 1,3-
Butylene glycol dimethacrylate (BD) 0.4
Part, 0.1 part allyl methacrylate (AMA) and 0.04 part cumene hydroperoxide (CHP). After the temperature was raised to 70 ° C., the reaction was continued for 60 minutes to complete the polymerization of the innermost layer polymer (A). Then M
MA 1.5 parts, BuA 22.5 parts, BD 1.0 parts and A
The monomer mixture forming the crosslinked elastic layer polymer (B) consisting of 0.25 part of MA was added and polymerized for 60 minutes to cover the innermost layer polymer (A) with the crosslinked elastic layer polymer (B). A two-layer crosslinked rubber elastic body was obtained. In this case, the amount of CHP used for the formation of the crosslinked elastic layer polymer (B) was 0.05% by weight with respect to the monomer mixture.

The swelling degree and gel content of the obtained two-layer crosslinked rubber elastic body were determined to be 10.0% and 90%, respectively. Subsequently, in order to form the intermediate layer polymer (D), MM
Using a mixture shown in Table 1 as a monomer mixture for reacting a mixture of A5 part, BuA5 part, BD5 part and AMA0.1 part, and finally forming the outermost layer polymer (C),
Various acrylic resin compositions were obtained. The resulting polymer emulsion is salted out with 5 parts of calcium chloride based on 100 parts of the polymer solid content, washed, dried and added with a stabilizer.
It was imprinted and various evaluations were performed. The residual amount of calcium and the gel content in the obtained final polymer are shown in Table 1.

Next, the obtained multilayer structure polymer was extruded under the following conditions to obtain 9 kinds of films. 40 mmφ (screw diameter) Extruder Resin temperature 245 ° C. Discharge amount 17 kg / hr (for thickness 50 mm) 50 kg / cm at 140 ° C. and 160 ° C. by sandwiching the obtained 9 kinds of laminated film and melamine resin impregnated paper ²
After 30 minutes of hot pressing, the film layer was cut with a cutter, and the adhesiveness was evaluated by whether or not the film could be peeled by hand. The results are shown in Table 2. From the results in Table 2, it is clear that the present acrylic resin composition has excellent adhesiveness with a coating agent such as a melamine resin. The appearance of the laminates obtained in Examples 1 to 7 after being subjected to an accelerated exposure test for 200 hours using an eye super UV tester was examined (Table 3), and the laminates of the present invention showed discoloration. It was revealed that there was a remarkable effect on the weather resistance. In the case of using the melamine-impregnated paper alone (Comparative Example 3), the color changed.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

EFFECT OF THE INVENTION Since the laminate of the present invention has extremely excellent weather resistance and impact resistance, it has become possible to use a thermosetting resin which has been difficult until now, and a vinyl chloride resin decorative board. It becomes possible to easily perform thermal bonding even with a thermoplastic resin such as, and its industrial significance is great.

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[Procedure amendment]

[Submission date] March 16, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025]

The present invention will be described in more detail with reference to the following examples. In the examples, "parts" means "parts by weight". Examples 1 to 7 (Production of acrylic resin composition) 250 parts of ion-exchanged water, 2 parts of ester soda salt of sulphosuccinic acid, and 0.05 parts of Rongalit (SFS) were charged in a polymerization vessel with a condenser, and stirred under nitrogen. After methyl methacrylate (MMA)
1.6 parts, butyl acrylate (BuA) 8 parts, 1,3-
Butylene glycol dimethacrylate (BD) 0.4
Part, 0.1 part allyl methacrylate (AMA) and 0.04 part cumene hydroperoxide (CHP). After the temperature was raised to 70 ° C., the reaction was continued for 60 minutes to complete the polymerization of the innermost layer polymer (A). Then M
MA 1.5 parts, BuA 22.5 parts, BD 1.0 parts and A
The monomer mixture forming the crosslinked elastic layer polymer (B) consisting of 0.25 part of MA was added and polymerized for 60 minutes to cover the innermost layer polymer (A) with the crosslinked elastic layer polymer (B). A two-layer crosslinked rubber elastic body was obtained. In this case, the amount of CHP used for the formation of the crosslinked elastic layer polymer (B) was 0.05% by weight with respect to the monomer mixture.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

Next, the obtained multilayer structure polymer was extruded under the following conditions to obtain 9 kinds of films. 40 mmφ (screw diameter) Extruder Resin temperature 245 ° C. Discharge amount 17 kg / hour (for thickness 50 μm ) 50 kg / at 140 ° C. and 160 ° C. sandwiching 9 kinds of the obtained laminated films and melamine resin impregnated paper cm ²
After 30 minutes of hot pressing, the film layer was cut with a cutter, and the adhesiveness was evaluated by whether or not the film could be peeled by hand. The results are shown in Table 2. From the results in Table 2, it is clear that the present acrylic resin composition has excellent adhesiveness with a coating agent such as a melamine resin. The appearance of the laminates obtained in Examples 1 to 7 after being subjected to an accelerated exposure test for 200 hours using an Eye Super UV tester was examined, and the appearance of the laminates of the present invention did not discolor and the weather resistance was improved. It was revealed that there was a remarkable effect. In the case of using the melamine-impregnated paper alone (Comparative Example 3), the color changed.

Claims (1)

[Claims] 1. A polymer comprising an innermost layer polymer (A), a crosslinked elastic layer polymer (B), an outermost layer polymer (C) and an intermediate layer polymer (D) shown below, which has a gel content of at least 50% and remains. A laminate in which an acrylic resin composition having a multilayer structure polymer having a metal content of 500 ppm or less is laminated on at least one surface of a thermosetting resin plate. Innermost layer polymer (A) 80 to 100 parts by weight of alkyl acrylate having an alkyl group of 1 to 8 carbon atoms and / or alkyl methacrylate (A ₁ ) having an alkyl group of 1 to 4 carbon atoms of 0 to 20 parts by weight monomers having a copolymerizable double bond (a ₂₎ a polyfunctional monomer of 0 parts by weight _{(a 3) (a 1)} 0 to 100 parts by weight of the total of ~ (a ₃₎ .1
5 parts by weight of the grafting agent obtained from the composition of (A _4), polymer crosslinked elastic layer polymer present in the core (B) alkyl acrylates having an alkyl group having 1 to 8 carbon atoms of 80 to 100 parts by weight (B ₁₎ a monomer having a copolymerizable double bond 0-20 parts by weight (B ₂₎ a polyfunctional monomer of 0 parts by weight _{(B 3) (B 1)} ~ (B 3 ) 0.1 to 100 parts by weight
Polymer present from the composition of 5 parts by weight of the graft crossing agent (B ₄ ) which is present outside the innermost layer polymer (A) Outermost layer polymer (C) 51 to 100 parts by weight of C1 to C4 Alkyl methacrylate (C ₁ ) 0.1 to 40 parts by weight of hydroxyalkyl (meth) acrylate (C ₂ ) having an alkyl group of 1 to 8 carbons 0 to 49 parts by weight of a monomer having a copolymerizable double bond obtained from the composition of the body (C _3), a polymer intermediate layer polymer present on the outer surface (D) 10 to 90 parts by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms (D ₁₎ 90 to 10 Alkyl methacrylate (D ₂ ) having 1 to 4 carbon atoms of an alkyl group 0 to 20 parts by weight of a monomer (D ₃ ) having a copolymerizable double bond 0 to 10 parts of polyfunctionality Monomer (D ₄ ) (D ₁ ) to (D ₄ ) 0.1 to 100 parts by weight
It is obtained from the composition of ₅ parts by weight of the graft crossing agent (D ₅ ), is present between the crosslinked elastic layer polymer (B) and the outermost layer polymer (C), and the amount of the alkyl acrylate (D ₁ ) is the crosslinked elastic layer. Polymer adjusted so as to monotonically decrease from the layer polymer (B) to the outermost layer polymer (C)