JPH03163152A - Multilayered polymer resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in transparency and stress whitening resistance by mixing a specified multilayered polymer with a thermoplastic resin. CONSTITUTION:99-1wt.% multilayered polymer comprising 5-35wt.% innermost layer polymer comprising 100 pts.wt. in total of 80-100 pts.wt. (1-8 C) alkyl acrylate (a1) and/or (1-4C) alkyl methacrylate (a2), 0-20 pts.wt. copolymerizable double bond-containing monomer (h) and 0-10 pts.wt. polyfunctional monomer (c) and 0.1-5 pts.wt. graft-crosslinking agent (d), 45-80wt.% crosslinked elastic polymer comprising 100 pts.wt. total of 80-100 pts.wt. component (a1)and 0-20pts. wt. component (b) and having a glass transition temperature <=0 deg.C, 5-40wt.% intermediate layer polymer comprising 100 pts.wt. total of 10-90 pts.wt. component (a1), 10-90 pts.wt. component (a2), 0-20 pts.wt. component (b), 0-10 pts.wt. component (c) and 0.1-5 pts.wt. component (d), and 10-40wt.% outermost layer polymer comprising 51-100 pts.wt. component (a1) and 0-49 pts.wt. component (b) and having a glass transition temperature >=60 deg.C is mixed with 1-99wt.% thermoplastic resin such as a polymer of a vinyl monomer or a vinylidene monomer of any one of formulas I-III (wherein X and Y are each H, Cl, Br, CH3 or the like; z is H, CF3 or the like; and R2 is fluoroalkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a multilayer structure polymer resin composition, more specifically, a multilayer structure polymer having excellent flexibility, transparency, and weather resistance mixed with a specific thermoplastic resin. Excellent transparency,
This invention relates to a multilayer structure polymer resin composition that has no or very little stress whitening property.

Generally, as a means to improve the impact resistance of thermoplastic resins, various attempts have been made to introduce so-called rubber components into the resins. The most common method for this is to introduce diene rubber, but since diene rubber has extremely poor weather resistance, this method is inappropriate for applications that require weather resistance.

In order to impart impact resistance without reducing weather resistance, various methods of blending acrylic rubber polymers have been studied, and the problem of weather resistance has been solved to some extent; however, such blend systems Significant stress whitening occurs, greatly reducing its commercial value, and the transparency that can be obtained is typically subject to limitations.

For example, polymethyl methacrylate (hereinafter abbreviated as PMMA), which has an extremely beautiful appearance and excellent weather resistance, is strongly desired to have improved impact resistance and elasticity. Attempts to introduce a rubber component into PMMA by simply copolymerizing the components have been proposed in the past, but in both cases, the introduction of a rubber component greatly reduces weather resistance, transparency, etc., and the appearance is poor. No satisfactory results have been obtained.

Several methyl methacrylate-based multilayer polymers containing acrylic rubber have been proposed so far, especially from the viewpoint of molding materials for films and sheets, but these have sacrificed transparency, which is an inherent characteristic of methyl methacrylate-based resins. Moreover, stress whitening resistance, which is a common drawback of impact-resistant resins, has hardly been improved.

In order to obtain a thermoplastic resin composition with excellent transparency, weather resistance, impact resistance, and stress whitening resistance, it is necessary to use a crosslinked elastic layer and a resin layer mainly composed of alkyl acrylate, which have been proposed so far. At present, a satisfactory thermoplastic resin composition cannot be obtained even by blending a simple multilayer polymer of the above with other thermoplastic resins.

In view of the current situation, the present inventors have made extensive studies to obtain a thermoplastic resin composition having the above-mentioned characteristics.
By blending a specific thermoplastic resin in a specific range with a multilayer polymer with a specific structure that has excellent flexibility, transparency, and weather resistance, it has excellent transparency and no stress whitening. Alternatively, the inventors have discovered that a thermoplastic resin composition with a very small amount can be obtained, and have arrived at the present invention.

That is, the present invention is a multilayer structure polymer resin composition comprising 99 to 1% by weight of the following multilayer structure polymer [I] and 1 to 99% by weight of the thermoplastic resin [■].

Multilayer structure polymer [■]: (A) 80 to 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and/or 1 to 4 carbon atoms
Alkyl methacrylate (A1) having an alkyl group of
, 0 to 20 parts by weight of a monomer having a copolymerizable double bond (A2), 0 to 10 parts by weight of a polyfunctional monomer (A3), and (A3)
) to (A3) in an amount of 0.1 to 5 parts by weight of a polymer of a graft cross-agent based on 100 parts by weight of the total amount, and the innermost layer polymer accounts for 5 to 35% by weight in the multilayer structure polymer. (A); (B) 80 to 100 parts by weight of an alkyl acrylate (B3) having an alkyl group having 1 to 8 carbon atoms; 0 to 20 parts by weight of a monomer having a copolymerizable double bond (B3); , 0 to 10 parts by weight of a polyfunctional monomer (Bl), and (B1
) to (B3) in an amount of 0.1 to 5 parts by weight based on the total amount of 100 parts by weight, the glass transition temperature is 0°C or less, and the proportion in the multilayer structure polymer is 45 to 80% by weight of a crosslinked elastic polymer (B); (C) 10 to 90 parts by weight of an alkyl acrylate (C3) having an alkyl group having 1 to 8 carbon atoms; 10 to 90 parts by weight of an alkyl acrylate having 1 to 8 carbon atoms; 4 alkyl group} (C*), 0 to 20 parts by weight of a monomer having a copolymerizable double bond (C3), 0 to 10 parts by weight of a polyfunctional monomer ( C4), and (C1
) to (C4) per 100 parts by weight of the total amount. One or more layers consisting of a polymer of 1 to 5 parts by weight of a graft cross-agent, in which the proportion of alkyl acrylate (C1) monotonically decreases from the crosslinked elastic polymer (B) to the outermost layer polymer (D). (D) an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (D3) in an amount of 51 to 100 parts by weight; ~49 parts by weight of a monomer (D2) having a copolymerizable double bond, having a glass transition temperature of 60°C or higher, and having a proportion of 10 to 40 parts by weight in the multilayer structure polymer. weight%
A multilayer structure polymer characterized in that the outermost layer polymer (D) is successively graft-bonded and has a gel content of 65% by weight or more.

Thermoplastic resin [II]: At least one polymer selected from the following groups (a) or (b), or a mixture of at least one polymer selected from each of the groups (a) and (b).

(a) The following formula: X / (at) CH* = C \ Y (wherein,
H. , COOH% COOCH! ,CN,OC
OCHI, COCH. ,C. H1so
s Represents H or OR'. However, Rl is a lower alkyl group) (a-) CF. =CFZ (in the formula, Z represents H, Cl2, F or CF3) or (a-) CHz = C-CO
A homopolymer of vinyl monomer or vinylidene monomer or a copolymer of these monomers represented by O R °C H s (in the formula, R2 represents a fluoroalkyl group).

(b) Polycarbonates, thermoplastic polyesters and polyamides.

The present invention will be explained in more detail below.

Innermost layer polymer (A) of multilayer structure polymer used in the present invention
The alkyl acrylate (A1) having an alkyl group having 1 to 8 carbon atoms may be linear or branched, and may be methyl acrylate, ethyl acrylate, probyl acrylate, butyl acrylate, 2-ethylhexyl acrylate. , n-octyl acrylate, etc. may be used alone or in combination, but those with a low glass transition temperature (hereinafter abbreviated as Tg) are more preferable. The alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms may be linear or branched, and methyl methacrylate, ethyl methacrylate, proyl methacrylate, butyl methacrylate, etc. are used alone or in combination. These alkyl (meth)acrylates (A1
) (which includes alkyl acrylate and alkyl methacrylate) is used in an amount of 80 to 100 parts by weight (hereinafter "parts by weight" is abbreviated as "part"). Furthermore, it is most preferable that these alkyl (meth)acrylates are made of the same monomer in all the multi-layer layers.
Depending on the final purpose, two or more types of monomers may be mixed,
Other types of (meth)acrylates may also be used.

Further, the monomer (A2) having a copolymerizable double bond is preferably an acrylic monomer other than the above, such as alkyl mech acrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, or methacrylic acid. It is used in a range of 0 to 20 parts. As the other component (A2), styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, etc. can be used in an amount not exceeding 20% by weight.

Furthermore, the polyfunctional monomer (A3) is preferably an alkylene glycol dimethacrylate such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate, and divinyl Benzene, polyvinylbenzene such as trivinylbenzene, alkylene glycol diacrylate, etc. can also be used. These monomers work effectively to crosslink the layer in which they are contained, but do not work on bonding between layers with other layers. Even if the polyfunctional monomer (A3) is not used at all, a fairly stable multilayer structure polymer can be obtained as long as the grafting agent is present, but it can be used as desired depending on the required physical properties. The amount used is 0-10
This is within the scope of the department.

On the other hand, as the graft cross-agent, allyl, methallyl or crotyl esters of copolymerizable α,β monounsaturated carboxylic acids or dicarboxylic acids, preferably allyl esters of acrylic acid, methacrylic acid, maleic acid and fumaric acid are used. However, allyl methacrylate has particularly excellent effects. In addition, triallyl cyanurate, triallyl isocyanurate, etc. can also be effectively used. In such a graft cross-agent, the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group or crotyl group, and is chemically bonded. During this time, a substantial portion of the allyl group, methallyl group, or crotyl group effectively functions in the polymerization of the next layer polymer (B) and provides a graft bond between the two adjacent layers.

The amount of grafting agent used is extremely important, and the amount of the grafting agent used is extremely important.
0.1 to 5 parts per 100 parts of the total amount of 1) to (A3),
It is preferably used in an amount of 0.5 to 2 parts. If the amount used is less than 0.1 part, the effective amount of graft bonding will be small, resulting in insufficient glabellar bonding. In addition, if the amount used exceeds 5 parts, the amount of reaction with the crosslinked elastic polymer (B) polymerized in the second stage becomes large, resulting in a two-layer crosslinked structure consisting of the polymer (A) and the polymer (B). This causes a decrease in the elasticity of the elastic body.

The innermost layer polymer (A) is a graft active layer, and its Tg
is set appropriately according to the required physical properties of the final polymer. Further, in general, it is advantageous in terms of quality that the crosslinking density is the same as, or even higher than, that of the crosslinked elastic polymer (B). Note that the innermost layer polymer (A) and the crosslinked elastic polymer (B) may have the same composition, but it is important that they have a two-layer elastic structure through two-stage polymerization rather than one-time charging. Moreover, it is advantageous that the catalyst amount, crosslinking density, etc. of the polymer (A) are higher than that of the polymer (A). The content of the innermost layer polymer (A) in the multilayer structure polymer is 5 to 35% by weight, preferably 5 to 25% by weight, and is 10 to 30% of the content of the crosslinked elastic polymer (B). The range is even more preferable. Next, the crosslinked elastic polymer (B) constituting the multilayer structure polymer is a main component that gives rubber elasticity to the polymer, and has an 80%
~100 parts of alkyl acrylate (Bl) having an alkyl group having 1 to 8 carbon atoms, 0 to 20 parts of a monomer (B2) having a copolymerizable double bond, 0 to 10 parts of polyfunctionality Total amount of monomer (B3) and (B1) to (B3) 10
0 parts to 0.1 to 5 parts of a grafting agent are polymerized.

As the alkyl acrylate (B.) having an alkyl group having 1 to 8 carbon atoms, the alkyl acrylates exemplified in (A3) can be used alone or in combination, and those with a low Tg are preferred.

As the monomer (B2) having a copolymerizable double bond, lower alkyl methacrylate is most preferable, but other monomers exemplified in (A2) can also be used.

Further, as the polyfunctional monomer (B3) and the grafting cross-agent, those exemplified for the innermost layer polymer (A) are also used.

The Tg of the crosslinked elastic body (B) alone needs to be 0°C or lower, preferably -20°C or lower, more preferably -
The temperature is below 30°C.

The content of crosslinked elastic polymer (B) in the multilayer structure polymer is 4
The amount is 5 to 80% by weight, and if it is less than 45% by weight, the desired flexibility cannot be obtained, whereas if it exceeds 80% by weight, the entire multilayer structure polymer becomes rubbery and difficult to handle.

The crosslinked elastic layer formed by graft bonding of the innermost polymer (A) and the crosslinked elastic polymer (B) has a gel content of 85% or more and a swelling degree in the range of 3 to 20. is preferred.

Furthermore, the intermediate layer (C) interposed between the crosslinked elastic polymer (B) and the outermost layer polymer contains 10 to 90 parts of carbon atoms having 1 to 8 carbon atoms.
an alkyl acrylate (C3) having an alkyl group of
10 to 90 parts of alkyl methacrylate (C2) having an alkyl group having 1 to 4 carbon atoms, 0 to 20 parts of a monomer (C3) having a copolymerizable double bond, 0 to 10 parts of polyfunctionality Total amount of monomers (C4), (C3) to (C4) 10
0 parts to 0.1 to 5 parts of a grafting agent are polymerized. Components (C1) to (C4) and the graft cross-agent are the same as the graft cross-agent used in the above-mentioned (A1) to (A3) and the innermost layer polymer (A), respectively. Also in the intermediate layer (C), the graft cross-agent is essential for closely bonding each polymer layer and obtaining excellent physical properties.

The intermediate layer may be one layer or 2H or more, but the alkyl acrylate (c1) ratio of each layer is determined by the crosslinked elastic polymer (
It is necessary to form each layer so as to gradually decrease from B) to the outermost layer polymer (D).

The content of the intermediate layer (C) in the multilayer structure polymer is 5 to 40
% by weight, preferably in the range 5-30% by weight. When the intermediate layer (C) consists of two or more layers, the content of each layer is preferably 5 to 25% by weight. When the ratio of the intermediate layer is 5% by weight without grooves, the function as an intermediate layer is not exhibited, and when it exceeds 40% by weight, the structure of the final polymer becomes unstable.

Furthermore, the outermost layer polymer (D) constituting the multilayer structure polymer is involved in distributing moldability, mechanical properties, etc. to the polymer, and the component (D3) that makes up this is as described above. The alkyl methacrylates exemplified in component (A1) are used, and the lower alkyl acrylates and the monomers exemplified as component (A2) described above are used alone or in combination as component (D2).

(D1) component is 51 to 100 parts, (D8) component is 0 to 4 parts
Each is used in a range of 9 parts.

In addition, the Tg of the outermost layer polymer (D) alone needs to be 60°C or higher in order to obtain excellent physical properties, and preferably 80°C or higher. The Tg of the polymer (D) alone is 60
If the temperature is below .degree. C., the final polymer described below will not have excellent physical properties even if the gel content is 65% or more.

The content of the outermost layer polymer (D) in the multilayer structure polymer is 10
~40% by weight. When the amount is less than 10% by weight, sufficient weather resistance cannot be obtained, and on the other hand, when it is used in excess of 40% by weight, the ratio of the crosslinked elastic layer decreases, resulting in insufficient flexibility.

Furthermore, the multilayer structure polymer used in the present invention needs to have a gel content of at least 65%,
Excellent properties such as transparency, weather resistance, and flexibility can only be imparted when this condition is met together with the above-mentioned special structure.

- In this case, the gel content refers to the entire two-layer crosslinked elastic body itself, and the graft components of the intermediate layer (C) and outermost layer polymer (D) to the crosslinked elastic body. Here, the gel content refers to a 1% by weight methyl ethyl ketone (hereinafter referred to as MEK) solution of the multilayer structure polymer prepared, and after being left at 25°C for a day and night, it was heated to 16.00O in a centrifuge.
r. p. m. This is the weight percent of insoluble matter after centrifugation for 90 minutes. The gel content is the added weight of the two-layer crosslinked elastic body and the grafted chains, and can be replaced by the grafting ratio, but in the present invention, since the polymer has a special structure, the gel content is This was used as a guideline for the amount of grafting.

Further, the gel content and degree of swelling of the two-layer crosslinked elastic body refer to values measured as follows.

A predetermined amount of the two-layer crosslinked elastic material was taken according to JIS K6388, immersed in MEK at 25°C for 48 hours to swell, then pulled out, the adhered MEK was wiped off, the weight was measured, and then the MEK was dried in a vacuum dryer. After drying and removing, read the absolute dry weight that has become constant and calculate it using the following formula.

When the degree of polymerization of the crosslinked elastic polymer (B) is increased to 1M as much as possible, a high impact strength is imparted to the final polymer.

Further, the glass transition temperature (Tg) as used in the present invention is calculated from the commonly known FOX formula: Tg Tg+ Tgx. In the formula, a1 and a2 each represent a weight fraction.

The multilayer structure polymer used in the present invention is usually obtained by a sequential multistage polymerization method using an emulsion polymerization method. Middle class (C
) in the case of multi-layer, alkyl acrylate}
Multi-stage polymerization may be carried out while gradually reducing the amount of -(C.). When carrying out a sequential multi-stage polymerization method using emulsion polymerization method, a predetermined amount of an emulsifier, a catalyst, a monomer, etc. are added to an aqueous solvent and reacted, and after each reaction, the monomers forming the upper layer and the polymerization are added. By sequentially adding an initiator to the reaction system, the multilayer structure polymer used in the present invention can be obtained.

There are no particular restrictions on the emulsifier, catalyst, etc. used in the production of the multilayer structure polymer, and emulsifiers, catalysts, etc. used in ordinary emulsion polymerization can be used. Typical examples of emulsifiers include anionic surfactants such as long-chain fatty acid salts, sulfonic acid salts, ester salts of sulfosuccinic acid, phosphate ester salts, and acid amide type anionic surfactants. Representative examples of catalysts include inorganic peroxides such as potassium persulfate, organic peroxides such as cumene hydroperoxide and lauroyl peroxide, and azo initiators such as azobisisobutyronitrile. Preferred examples include redox initiators such as cumene hydroperoxide dosodium formaldehyde sulfoxylate.

The temperature conditions and polymerization time for polymerization of multilayer polymers depend on the catalyst used, etc., and any conditions are possible as long as the polymerization proceeds smoothly to the final stage, but usually is polymerized within the temperature range of 30-95°C, and the polymerization time is 3-20 hours. Note that it is often preferable to polymerize the crosslinked elastic body portion of the polymer at a relatively low temperature.

Furthermore, the method for producing the multilayer structure polymer used in the present invention is not particularly limited to the above method; for example, after emulsion polymerization,
It can also be obtained by an emulsion suspension polymerization method in which polymerization of the outermost layer is converted to suspension polymerization.

There is no particular restriction on the emulsion particle size in the final polymer of the multilayer structure polymer, but it is between 800 and 2.0
The most preferable range is about 00 people.

Latex, which is a multilayer polymer, is made into a powder by adding additives such as antioxidants, lubricants, and coagulants as necessary and salting it out, followed by filtering, washing with water, dehydration, and drying. It is considered to be a polymer of

As explained above, the basic polymer structure of the multilayer structure polymer used in the present invention has the following characteristics.

(1) The crosslinked elastic layer has a two-layer elastic structure containing the innermost polymer (A) as an inner layer, (2) The Tg of the crosslinked elastic layer is 0°C or less, and the Tg of the outermost layer is 60°C or higher. that it was set to .

(3) The proportion of the crosslinked elastic layer (including the innermost layer) in the polymer is 50% by weight or more.

(4) At least one intermediate layer is arranged in such a manner that the ratio of alkyl acrylate in each layer monotonically decreases from the crosslinked elastic layer to the outermost layer between the crosslinked elastic layer and the outermost layer; ) By chemically grafting the layers between each layer using a grafting agent, (6) By ensuring that the gel content of the final polymer is 65% by weight or more, by satisfying all of these requirements. This is the first time that the multilayer structure polymer used in the present invention can satisfy all the basic characteristics of the multilayer structure polymer, which is extremely flexible and has excellent transparency and weather resistance, and these requirements. If you multiply even just one, you won't get anything satisfactory. In particular, the multilayer structure polymer used in the present invention is characterized in that the crosslinked elastic body is a two-layer structure elastic body containing the innermost layer polymer as an inner layer, and as a result, it maintains excellent weather resistance. It becomes possible to impart excellent elastic properties to the polymer while maintaining the elasticity.

In other words, although acrylic rubber generally has superior weather resistance compared to diene rubber, it has slow elastic recovery, large deformation under stress, and low rubber efficiency, and conventional elastic structures consisting of only one layer sacrifice weather resistance. There was a limit to the ability to impart elastic properties to the core, but by providing the innermost layer (A) in the core and polydispersively relieving the stress concentrated in the crosslinked elastic layer (B), Further elasticity can be imparted without sacrificing weather resistance.

The multilayer structure polymer resin composition of the present invention contains 99 to 1 part by weight of the multilayer structure polymer [I] and the above-mentioned polymer (a) or (
Produced by blending 1 to 99 parts by weight of at least one polymer selected from group b) or a mixed part of at least one polymer selected from each group of polymers (a) and (b). .

When the above-mentioned multilayer structure polymer is mixed with other compatible thermoplastic resins having different refractive indexes, it is possible to form a resin composition with excellent transparency and no or very little stress whitening property. . In particular, when blended with a methyl methacrylate resin, a resin composition can be obtained that has excellent transparency, stress whitening resistance, weather resistance, and impact resistance.

It is surprising that stress whitening properties are extremely low even in polymer blend systems. This is based on the effect of the special structure of the multilayer polymer, and cannot be predicted from conventional methods of introducing rubber components.

To explain the polymer blend system in more detail, for example, when mixed with vinyl chloride resin, polystyrene, AS resin, polycarbonate, etc., the multilayer structure polymer used in the present invention has a type of weather resistance and impact resistance. Acts as a modifier and significantly improves weather resistance and impact resistance.

In addition, blend compositions containing polyvinylidene fluoride have excellent properties such as weather resistance, transparency, stress whitening resistance, chemical resistance, toughness, and moldability. A resin composition comprising 50 to 99 parts of a multilayer structure polymer is also excellent as a material for film molding, and provides a transparent, tough film with excellent weather resistance, stress whitening resistance, chemical resistance, etc. Such a film can easily impart weather resistance and a design effect by laminating the surface of an ordinary shaped article, and has extremely high commercial value.

The present invention will be specifically explained below using Examples.

Note that all parts in the examples are parts by weight. Furthermore, the abbreviations used in the examples are as follows.

MMA: Methyl methacrylate BuA: Butyl acrylate BD: 1.3-butylene dimethacrylate AMA: Allyl methacrylate C} {P: Cumene hydroperoxide SFS: Sodium formaldehyde sulfoxylate n-OSH: n-butylene dimethacrylate Example 1 250 parts of ion-exchanged water, 2 parts of sulfosuccinic acid ester soda salt, SFS O. After stirring under a nitrogen stream, the temperature was raised to 70'C. Then 9 parts of BuA. A monomer mixture consisting of 0.6 parts of MMA, 0.4 parts of BD, and 0.05 parts of CHP was charged, and the reaction was continued for 60 minutes to complete the polymerization of layer (A). Subsequently, 65 parts of BuA. A monomer mixture consisting of 0.455 parts of AMA and 0.15 parts of CHP was added over 60 minutes and maintained for an additional 60 minutes to polymerize a crosslinked elastic body consisting of two layers (A) and (B). The crosslinked elastic body thus obtained had a gel content of 94% and a degree of swelling of 12. Furthermore, the glass transition temperature (Tg) of layer (B) was -40°C. Next, 3.5 parts of MMA, which corresponds to the middle class, and 3.5 parts
part BuA, 0.07 part AMA and 0.05 part CH
A monomer mixture consisting of P was added over a period of 30 minutes to polymerize, and finally 17 parts of MMA, 1 part of BuA. 0.
18 parts of n-OSH. The outermost layer polymer (D) consisting of 0.1 part of CHP was polymerized in the same manner to obtain a multilayer structure polymer latex. The Tg of layer (D) was 90°C.
This latex was salted out using 5 parts of calcium chloride, filtered through an oven, washed with water, dehydrated and dried to obtain a bow-shaped multilayered polymer. The gel content of the polymer was 88%.

75 parts of this multilayer structure polymer, 25 parts of polyvinylidene fluoride
and 1.5 parts of an ultraviolet absorber were mixed and extruded at 190° C. using an extruder with a screw having a diameter of 40 mm, and the pellets were cut into pellets.

A film with a thickness of 100P was formed from this pellet by the T-Guy method using the same extruder. Furthermore, it was possible to form a thin film of about 20P using this pellet by changing the film forming conditions. The resulting 1001J7+1 film had a total light transmittance of 92.5% and a haze value of 1.7. In addition, the tensile modulus at 20°C is 1,500 kg/Cm",
The elongation at break was 400% (measured at an elongation rate of 100%/min). Furthermore, this film was laminated onto a commercially available PVC steel plate using a heat-pressure bonding method, and its weather resistance was evaluated in an accelerated exposure test using a sunshine weather meter. Commercially available PVC steel sheets were considerably discolored after 500 hours, but those laminated with the film obtained from the product of the present invention had a discoloration of 2.00 hours.
There was no discoloration at all even after 0 hours.

Claims (1)

[Scope of Claims] A multilayer structure polymer resin composition comprising 99 to 1% by weight of the following multilayer structure polymer [I] and 1 to 99% by weight of a thermoplastic resin [II]. Multilayer structure polymer [I]: (A) 80 to 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and/or 1 to 4 carbon atoms
Alkyl methacrylate (A_1
), 0 to 20 parts by weight of a monomer having a copolymerizable double bond (A_2), 0 to 10 parts by weight of a polyfunctional monomer (A_3), and (A
0.1 per 100 parts by weight of the total amount of _1) to (A_3)
Innermost layer polymer (A) consisting of ~5 parts by weight of a polymer of a graft cross-agent and accounting for 5 to 35% by weight in the multilayer structure polymer: (B) 80 to 100 parts by weight of carbon number 1 Alkyl acrylate having ~8 alkyl groups (B_1), 0 to 20 parts by weight of a monomer having a copolymerizable double bond (B_2), 0 to 10 parts by weight of a polyfunctional monomer (B_3) , and (B
0.1 per 100 parts by weight of the total amount of _1) to (B_3)
A crosslinked elastic polymer (B) consisting of a polymer of ~5 parts by weight of a grafting cross-agent, having a glass transition temperature of 0° C. or lower, and having a proportion of 45 to 80% by weight in the multilayer structure polymer.
: (C) 10 to 90 parts by weight of alkyl acrylate (C_1) having an alkyl group having 1 to 8 carbon atoms, 10 to 90 parts by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (C_2), 0 to 20 parts by weight of a monomer having a copolymerizable double bond (C_3), 0 to 10 parts by weight of a polyfunctional monomer (C_4), and (C
0.1 per 100 parts by weight of the total amount of _1) to (C_4)
~ 5 parts by weight of a polymer of a graft cross-agent, one or more layers in which the proportion of alkyl acrylate (C_1) decreases monotonically from the crosslinked elastic polymer (B) to the outermost layer polymer (D). Therefore, the proportion of the multilayer structure polymer is 5.
-40% by weight of intermediate layer (C): (D) 51-100 parts by weight of alkyl methacrylate (D_1) having alkyl groups having 1-4 carbon atoms, 0-49 parts by weight of copolymerizable double bonds; The monomer (D_2) has a glass transition temperature of 60°C or higher, and the proportion in the multilayer structure polymer is 10 to 40% by weight.
A multilayer structure polymer in which the outermost layer polymer (D) is successively graft-bonded and has a gel content of 65% by weight or more. Thermoplastic resin [II]: At least one polymer selected from the following groups (a) or (b), or a mixture of at least one polymer selected from each of the groups (a) and (b). (a) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X and Y are H, Cl, Br, F, CH, respectively.
_3, COOH, COOCH_3, CN, OCOCH_
3, COCH_3, C_8H_5, SO_3H or OR
Represents ^1. However, R^1 is a lower alkyl group) (a_2) CF_2:CFZ (In the formula, Z represents H, Cl, F, or CF_3) or (a_3) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (Formula A homopolymer of a vinyl monomer or a vinylidene monomer, or a copolymer of these monomers, represented by (R^2 represents a fluoroalkyl group). (b) Polycarbonates, thermoplastic polyesters and polyamides.