JPS6320459B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel acrylic thermoplastic resin composition that is transparent and highly flexible. More specifically, it has a special tapered structure between a crosslinked elastic polymer layer (inner layer) having a two-layer structure and a resin layer (outer layer) with a glass transition temperature (hereinafter abbreviated as Tg) of 60°C or higher. At least one kind of multilayer structure polymer [ ] with excellent transparency, weather resistance, solvent resistance, stress whitening resistance, processability, etc. and a basic polymer structure in which the resin layer is in a predominant amount relative to the crosslinked elastic polymer layer. is obtained by blending the multilayer structure polymer [ ] with at least one transparent and flexible multilayer structure polymer [ ] that has a crosslinked elastic polymer layer that is almost equal to or larger than the resin layer. This invention relates to a novel acrylic thermoplastic resin composition that is transparent and highly flexible, and has excellent weather resistance, solvent resistance, stress whitening resistance, processability, etc. Acrylic resins, particularly methyl methacrylate polymers, are known as resins that have both excellent transparency and weather resistance, and are widely used in cast molded products, extrusion molded products, and the like. However, it is widely known that these methyl methacrylate polymers are generally hard and brittle, making them unsuitable as materials for films and sheets, and that they cannot be used in applications that require flexibility. This is what happened. For this reason, a number of attempts have been made to introduce certain rubber components into methyl methacrylate polymers in order to impart toughness and flexibility, but these have resulted in significant reductions in weather resistance. However, the appearance of methyl methacrylate polymers has deteriorated due to a significant decrease in transparency. Not successful. Furthermore, from the viewpoint of film sheet materials, several methyl methacrylate-based multilayer polymers containing acrylic rubber have been proposed. However, most of these multilayer structured polymers sacrifice the inherent characteristics of methyl methacrylate polymers, such as transparency and weather resistance, in order to impart toughness and flexibility, and are not satisfactory. Furthermore, in these multilayer polymers, flexibility and toughness are contradictory to other properties such as processability (fluidity), weather resistance, and solvent resistance due to constraints on the polymer structure. There are limits to how much flexibility can be added without sacrificing properties. For this reason, even if it is possible to provide flexibility and toughness to the extent that it is not difficult to handle it as a material for films and sheets, the current situation is that it cannot be used for applications that require even greater flexibility. . In view of the current situation, the present inventors developed an acrylic-based material that has excellent stress whitening resistance and solvent resistance, as well as arbitrary flexibility, without sacrificing transparency, weather resistance, and processability. As a result of intensive studies to obtain a polymer, we found a crosslinked elastic polymer layer (inner layer) mainly composed of acrylic acrylate with a two-layer structure and a resin layer mainly composed of alkyl methacrylate with a Tg of 60℃ or higher. (outer layer) and at least one intermediate layer containing alkyl acrylate and alkyl methacrylate as main components and in which the amount of alkyl acrylate monotonically decreases from the crosslinked elastic polymer layer to the resin layer. , and at least one type of multilayer structure polymer [ ] that is transparent and has excellent weather resistance, solvent resistance, stress whitening resistance, processability, etc., and a base polymer in which the resin layer has a predominant amount relative to the crosslinked elastic polymer layer. The structure is the same as the multilayer structure polymer [], but
The object of the present invention can be achieved by blending at least one type of transparent, particularly flexible, multilayer structure polymer containing a crosslinked elastic polymer layer in an amount approximately equal to or greater than that of the resin layer. They discovered this and arrived at the present invention. The gist of the present invention is a first invention comprising a thermoplastic resin composition comprising 1 to 99 parts by weight of at least one kind of multilayer structure polymer [] and 99 to 1 part by weight of at least one kind of multilayer structure polymer []. 1 to 99 parts by weight of at least one kind of multilayer structure polymer [] and 99 to 1 part of at least one kind of multilayer structure polymer []
A resin compound consisting of 1 to 99 parts by weight of the following:
99 to 1 part by weight of at least one polymer selected from group (i) or (ii), or a mixture of at least one polymer selected from each of groups (i) and (ii); The second invention is a thermoplastic resin composition comprising: Polymer (i): A homopolymer of a monomer having the following general formula (a), (b) or (c) or a copolymer consisting of two or more of these monomers. CH ₂ = CXY ... (a) However, in the formula, X and Y are H, Cl, F, Br, CH ₃ ,
It is either COOH, COOCH ₃ , CN, OCOCH ₃ , C ₆ H ₅ , an alkoxy group, OCCH ₃ or SO ₃ H. CF ₂ =CFZ...(b) However, Z in the formula is either H, F, Cl, or CF ₃ . However, in the formula, R is a fluoroalkyl group. Polymer (ii): polycarbonate, thermoplastic polyester, polyamide. In the present invention, the multilayer structure polymer [] and the multilayer structure polymer [] have the following polymer structures. Multilayer structure polymer []: 80 to 100 parts by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (A ₁ ), 0 to 20 parts by weight of a copolymer A monomer having a polymerizable double bond (A ₂ ), 0 to 10 parts by weight of a polyfunctional monomer (A ₃ ), based on 100 parts by weight of the total amount of (A ₁ ) to (A ₃ ) 0.1
~5 parts by weight of a graft cross-agent, the proportion of which in the multilayer structure polymer is 5 to 35% by weight, the innermost polymer (A), and 80 to 100 parts by weight of a carbon number of 1 to 8. Alkyl acrylate having an alkyl group (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 ) , 0.1 per 100 parts by weight of the total amount of (B ₁ ) to (B ₃ )
A crosslinked elastic polymer (B) consisting of ~5 parts by weight of a grafting agent and having a proportion of 10 to 40% by weight in the multilayer polymer [], 51 to 100 parts by weight of a carbon number of 1 to 4 of alkyl methacrylate (C ₁ ) and (C ₂ ) having 0 to 49 parts by weight of copolymerizable double bonds, the Tg is at least 60°C, and the proportion in the multilayer structure polymer [] is at least 60°C. The outermost layer polymer (C) is 50 to 80% by weight, and the basic structural unit is 10 to 90 parts by weight of carbon number 1 as an intermediate layer (D) between the polymer (B) layer and the polymer (C) layer. Alkyl acrylate (D ₁ ) having ~8 alkyl groups, 90 to 10 parts by weight of alkyl methacrylate (D ₂ ) having alkyl groups having 1 to 4 carbon atoms, 0 to 20 parts by weight of copolymerizable double bonds 0.1 to 100 parts by weight of the total amount of the monomer (D ₃ ), 0 to 10 parts by weight of the polyfunctional monomer (D ₄ ), and (D ₁ ) to (D ₄ ).
An intermediate layer (D) consisting of a composition of ~5 parts by weight of a graft cross-agent, in which the amount of alkyl acrylate in the intermediate layer (D) monotonically decreases from the crosslinked elastic polymer (B) to the outermost layer polymer (C). ), and the gel content of the multilayer polymer is at least 50%. Multilayer structure polymer []: 80 to 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (A ₁ '), 0 to 20 parts by weight Monomer having a copolymerizable double bond (A ₂ ′), 0 to 10 parts by weight of polyfunctional monomer (A ₃ ′), total amount of (A ₁ ′) to (A ₃ ′) 0.1 per 100 parts by weight
Innermost layer polymer (A') consisting of ~5 parts by weight of a graft cross-agent and occupying a proportion of 5 to 40% by weight in the multilayer structure polymer [], 80 to 100 parts by weight of a carbon number of 1 to 100%; Alkyl acrylate (B ₁ ′) having 8 alkyl groups, 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 0.1 per 100 parts by weight of the total amount of (B ₃ ′), (B ₁ ′) to (B ₃ ′)
A crosslinked elastic polymer (B') consisting of ~5 parts by weight of a grafting agent and having a proportion of 30 to 80% by weight in the multilayer polymer [], 51 to 100 parts by weight of a carbon number of 1 to _A multilayered _polymer [ ] The outermost layer polymer (C′), which accounts for 10% by weight or more and less than 50% by weight, is the basic structural unit, and an intermediate layer (D) is formed between the polymer (B′) layer and the polymer (C′) layer. 10 to 90 parts by weight of an alkyl acrylate having an alkyl group of 1 to 8 carbon atoms (D ₁ ′), 90 to 10 parts by weight of an alkyl methacrylate having an alkyl group of 1 to 4 carbon atoms (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 ′), (D ₁ ′) to ( D ₄ ′) 0.1 per 100 parts by weight
The intermediate layer (D') has a composition of ~5 parts by weight of a grafting agent, and the amount of alkyl acrylate in the intermediate layer (D') decreases monotonically from the crosslinked elastic polymer (B') to the outermost layer polymer (C'). A multilayer structure polymer having at least one layer (D'). The features of the present invention are transparency, weather resistance,
A multilayer polymer with excellent stress whitening resistance, solvent resistance, and processability; and a multilayer polymer with excellent flexibility, slightly inferior processability, and excellent transparency, weather resistance, and stress whitening resistance. By blending [], a thermoplastic resin composition can be obtained that has excellent transparency, weather resistance, flexibility, and processability that could not be obtained with conventional multilayer polymers alone. Multilayer structure polymer [ ] and multilayer structure polymer [ ] have the same basic polymer structure, and both have the following characteristics. That is, (1) the crosslinked elastic polymers (B) and (B') have a two-layer elastic structure containing the innermost layer polymers (A) and (A'), respectively, and (2) the resin layer. (3) The ratio of alkyl acrylate between the crosslinked elastic polymer layer and the outermost polymer layer is monotonous from the crosslinked elastic polymer layer to the outermost polymer layer. (4) Chemically grafting the interlayers using a grafting agent; (5) The gel content of the final polymer is at least 50% %. By satisfying all of these requirements, multilayer polymers [] and [] have transparency, weather resistance,
For the first time, the basic characteristics of the multilayer structure polymer composition used in the present invention, which are excellent stress whitening resistance and solvent resistance, can be satisfied, and if even one of these requirements is lacking, a satisfactory product cannot be obtained. In particular, the multilayer structure polymers [ ] and [ ] of the present invention are characterized in that the crosslinked elastic polymer layer is composed of a two-layer elastic body structure containing the innermost layer polymer as an inner layer. In general, acrylic rubber has superior weather resistance compared to diene rubbers, etc., but on the other hand, elastic recovery is slow, deformation due to stress is large, and rubber efficiency is low. That is, there is a limit to the elastic body structure consisting of only one layer obtained by conventional one-stage polymerization in order to provide various properties such as solvent resistance and water whitening resistance as described above while maintaining excellent weather resistance. In order to solve these drawbacks, the multilayer structure polymers [] and [] used in the present invention have the innermost layer polymers (A) and (A') in the core of the crosslinked elastic polymers (B) and (B'). ) exist, respectively.
The presence of the innermost layer polymers (A) and (A') polydispersively relieves the stress concentrated on the crosslinked elastic polymer (B) and (B') layers when stress is applied, As a result, the incidence of microvoids increases and excellent impact resistance is provided even without apparent stress whitening. In the case of multilayer polymer [], the ratio of the resin layer is set to be higher than that of the crosslinked elastic polymer layer, so although the flexibility is slightly lacking, it has characteristics such as weather resistance and solvent resistance. Not only that, but by keeping the gel content of the final polymer below 80%, it also has excellent processability. The alkyl acrylate having an alkyl group having 1 to 8 carbon atoms constituting the innermost layer polymer (A) of the multilayer structure polymer [] may be linear or branched, and may be methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, 2
- Ethylhexyl acrylate, n-octyl acrylate, etc. can be used alone or in combination.
Those with low Tg are more preferable. Also, the number of carbon atoms is 1~
The alkyl methacrylate having 4 alkyl groups may be linear or branched, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. are used alone or in combination. These alkyl (meth)acrylates (A ₁ ) are used in an amount of 80 to 100 parts by weight. In addition, it is most preferable that these alkyl (meth)acrylates are used uniformly in all the multilayer layers, but depending on the final purpose, two or more types of monomers may be mixed, or different types of (meth)acrylates may be used. It's okay to be hit. In addition, the monomer (A ₂ ) having a copolymerizable double bond is lower alkyl acrylate, lower alkoxy acrylate, cyanoethyl acrylate,
Acrylic monomers such as acrylamide, acrylic acid, and methacrylic acid are preferred, and are used in an amount of 0 to 20 parts by weight. In addition, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, etc. can be used in an amount not exceeding 20% by weight in component (A). Furthermore, the polyfunctional monomer (A ₃ ) 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 divinylbenzene , polyvinylbenzene such as trivinylbenzene, alkylene glycol diacrylate, and the like can also be used. These monomers are effective in bridging the layer in which they are contained,
It does not affect interlayer bonding with other layers.
Even if the polyfunctional monomer (A ₃ ) is not used at all, it will give a fairly stable multilayered polymer as long as the grafting agent is present, but it can be used arbitrarily depending on the required physical properties, but the amount used may vary. ranges from 0 to 10 parts by weight. On the other hand, the grafting agent is a copolymerizable allyl, methallyl or crotyl ester of α,β-unsaturated carboxylic acid or dicarboxylic acid, preferably acrylic acid,
Allyl esters of methacrylic acid, maleic acid and fumaric acid are used, with allyl methacrylate being particularly effective. In addition, triallyl cyanurate, triallyl isocyanurate, etc. can also be effectively used. Such graft cross-agents are chemically bonded primarily because the conjugated unsaturated bonds of their esters react much faster than allyl, methallyl, or crotyl groups. During this time, a substantial portion of the allyl group, methallyl group, or crotyl group acts effectively during the polymerization of the next layer to provide a graft bond between two adjacent layers. The amount of graft cross-agent used is extremely important, and is 0.1 parts by weight per 100 parts by weight of the total amount of components (A ₁ ) to (A ₃ ) above.
It is used in an amount of 5 parts by weight, preferably 0.5 to 2 parts by weight. If the amount used is less than 0.1 part by weight, the effective amount of graft bonding will be small and the bonding between layers will be insufficient. In addition, if the amount used exceeds 5 parts by weight, the amount of reaction with the crosslinked elastic polymer (B) formed in the second stage polymerization becomes large, resulting in a two-layer crosslinked structure consisting of polymer (A) and 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 appropriately set depending on the physical properties required of the final polymer. 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). It is possible that the innermost layer polymer (A) and the crosslinked elastic polymer (B) have the same composition, but it is important that they are made into a two-layered elastic body structure through two-stage polymerization, rather than being charged at one time. However, it is advantageous to set the catalyst amount, crosslinking density, etc. higher for the polymer (A). Considering the initial polymerizability, the presence of the innermost layer polymer (A) is extremely important in order to obtain a stable multilayer structure polymer, and the amount of catalyst is generally charged in the largest amount in each polymer layer. The use of a grafting cross-agent is essential for effectively synthesizing a two-layer elastic structure that is chemically bonded to the crosslinked elastic polymer (B) formed in the second stage. Without this graft bond, the two-layer elastomer structure would easily undergo phase destruction during melt molding, resulting in a decrease in rubber efficiency and failing to exhibit the desired excellent weather resistance, stress whitening resistance, etc. The content of the innermost layer polymer (A) in the multilayer structure polymer is 5 to 35% by weight, preferably 5 to 15% by weight, and is preferably lower than the content of the crosslinked elastic polymer (B). Next, the crosslinked elastic polymer (B) constituting the multilayer structure polymer [] is the main component that gives rubber elasticity to the polymer [], and contains 80 to 100 parts by weight of carbon atoms 1 to 8.
Alkyl acrylate having an alkyl group (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 ₁ ) to (B ₃ ) in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the grafting agent. As the alkyl acrylate (B ₁ ) having an alkyl group having 1 to 8 carbon atoms, the alkyl acrylates exemplified in (A ₁ ) mentioned above may be used alone or in combination, but those with a low Tg are more preferable. Monomer with copolymerizable double bond (B ₂ )
The most preferred is lower alkyl methacrylate, and the same monomers as exemplified for (A ₂ ) can also be used. Further, as the polyfunctional monomer (B ₃ ) and graft cross-agent, those exemplified in the innermost layer polymer (A) are used. The Tg of the crosslinked elastic polymer (B) alone is 0°C or lower, preferably -30°C or lower to provide good physical properties. The content of the crosslinked elastic polymer (B) in the multilayer structure polymer [] is preferably in the range of 10 to 40% by weight, and is preferably higher than the content of the innermost layer polymer (A). In this way, the innermost layer polymer (A) and crosslinked elastic polymer (B)
Because it has a two-layer cross-linked elastic body consisting of a two-layer elastic body structure in which the two rubbers are graft-bonded, it has become possible to simultaneously satisfy various properties that could not be achieved with conventional single-system rubbers. The gel content of this two-layer crosslinked elastic body was determined by the following measurement method.
In order to obtain excellent physical properties, it is necessary to set the swelling degree to 85% or more and the degree of swelling to be in the range of 3 to 13. (Method for measuring gel content and degree of swelling) A predetermined amount of the two-layer crosslinked elastic material was sampled according to JIS K-6388, and methyl ethyl ketone (hereinafter referred to as
Abbreviated as MEK. ), immerse it in water to swell, then pull it out, wipe off the adhered MEK, and measure its weight.
After that, MEK is removed by drying in a vacuum dryer, and the absolute dry weight, which has reached a constant weight, is read and calculated using the following formula. Swelling degree = Weight after MEK swelling - Bone dry weight / Bone dry weight Gel content (%) = Bone dry weight / Weight of collected sample x 100 Generally, the degree of polymerization of the crosslinked elastic polymer (B) should be as high as possible to reduce the final weight. Gives high impact strength to the combination.
On the other hand, for the core innermost layer polymer (A), this is not the case; rather, a large amount of catalyst is used to stabilize the initial polymerization including particle formation, and a large amount of graft active groups are used. The performance as a two-layer crosslinked elastic body tends to be good. Furthermore, the outermost layer polymer (C) constituting the multilayer structure polymer [] is involved in distributing moldability, mechanical properties, etc. to the polymer [], and constitutes (C ₁ ) The components include the alkyl methacrylate exemplified in the component (A ₁ ) mentioned above, and (C ₂ )
As the components, lower alkyl acrylates and the monomers exemplified as component (A ₂ ) mentioned above are used alone or in combination. (C ₁ ) component is 51 to 100 parts by weight, (C ₂ ) component is 0
~49 parts by weight, respectively. The Tg of the outermost layer polymer (C) alone needs to be 60°C or higher, preferably 80°C or higher in order to obtain excellent physical properties. The Tg of the polymer (C) alone is 60
If the temperature is below .degree. C., even if the gel content of the final polymer (described later) is 50% or more, it will not have excellent physical properties. The content of the outermost layer polymer (C) in the multilayer structure polymer is 50 to 80% by weight. The multilayer structure polymer [] used in the present invention has the above-mentioned innermost layer polymer (A), crosslinked elastic polymer (B), and outermost layer polymer (C) as basic structural units, and further includes the polymer (B) layer. and 10 to 90 parts by weight of carbon atoms 1 to 8 between the polymer (C) layers.
Alkyl acrylate (D ₁ ) having an alkyl group of from 90 to 10 parts by weight, alkyl methacrylate (D ₂ ) having an alkyl group having 1 to 4 carbon atoms, 0 to 10 parts by weight
20 parts by weight of copolymerizable double bond (D ₃ ), 0-
10 parts by weight of polyfunctional monomers ( _D4 ), ( _D1 ) to ( _D4 )
The intermediate layer (D) is composed of 0.1 to 5 parts by weight of a grafting agent based on 100 parts by weight of the total amount of the polymer (B). At least one layer is arranged so as to monotonically decrease toward the combined (C) layer. Here, the components (D ₁ ) to (D ₄ ) and the grafting agent are (B ₁ ), (C ₁ ), (A ₂ ), (A ₃ ) and the innermost layer polymer, respectively.
It is similar to the graft cross-agent used in (A). The grafting agent used in the intermediate layer (D) is essential for tightly bonding each polymer layer and obtaining excellent physical properties. The content of each intermediate layer (D) in the multilayer structure polymer [] is 5 to 35% by weight, preferably 5 to 25% by weight, and if it is less than 5% by weight, it will not lose its function as an intermediate layer. If it exceeds 35% by weight, the balance of the final polymer will be disturbed, which is not preferable. Furthermore, the multilayer structure polymer used in the present invention []
has a gel content of at least 50%, preferably at least 60%, which, together with the above-mentioned special structure, provides excellent properties such as stress whitening resistance, impact resistance, solvent resistance, water whitening resistance, etc. . In this case, the gel content includes the two-layer crosslinked elastic body itself and the graft components of the intermediate layer (D) and the outermost layer polymer (C) to the crosslinked elastic body. is 1% by weight of the multilayer polymer [ ]
This is the weight percent of the insoluble matter after a MEK solution was prepared, left overnight at 25°C, and then centrifuged at 16,000 rpm for 90 minutes using a centrifuge. The component of the gel content is the added weight of the two-layer crosslinked elastic body and the grafted chains, and it can also 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. From the point of view of solvent resistance, the higher the gel content, the more advantageous it is, but from the point of view of easy moldability, the presence of a certain amount or more of free polymer is necessary, so the upper limit of the gel content is about 80%. preferable. On the other hand, the basic polymer structure of multilayer structure polymer [] is the same as multilayer structure polymer [], but the ratio of each layer is set so that the crosslinked elastic polymer layer is almost in a predominant amount compared to the resin layer. . Therefore, compared to the multilayer structure polymer [], the amount of free polymer is lower, so the processability is slightly lower, but the flexibility is extremely excellent. In addition, since the polymer has the above-mentioned structural characteristics, even if the crosslinked elastomer component increases, properties such as transparency, weather resistance, and stress whitening resistance hardly deteriorate. Innermost layer polymer (A′) of multilayer structure polymer []
The components (A ₁ ′), (A ₂ ′), (A ₃ ′) and the graft cross-agent are each component ( _A1 ),
The same ones as (A ₂ ), (A ₃ ) and grafting cross-agents are used. Innermost layer polymer (A′) of multilayer structure polymer []
The amount of the graft cross-agent is also very important, and is used in the range of 0.1 to 5 parts, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the above-mentioned components (A ₁ ') to (A ₃ '). If the amount is less than 0.1 part by weight, the effective amount of graft bonding will be small and the bonding between the layers will be insufficient.
Further, if the amount exceeds 5 parts by weight, the amount of reaction with the crosslinked elastic polymer (B) polymerized in the second stage becomes large, and the elasticity of the two-layer crosslinked rubber elastic body having a two-layer elastic body structure decreases. The innermost layer is a polymer (A') or a graft active layer, and its Tg is appropriately set according to the physical properties required of the final polymer. In addition, its crosslink density is generally the same as that of the crosslinked elastic polymer (B′), or
In fact, the higher the price, the more advantageous it is in terms of quality. Although it is possible that the innermost layer polymer (A') and the crosslinked elastic polymer (B') have the same composition, it is important to create a two-layer elastic body structure through two-stage polymerization rather than one-time charging. However, it is advantageous for the polymer (A') to have a higher catalyst amount, crosslinking density, etc. Considering the initial polymerization, the innermost layer polymer (A′)
The presence of catalytic acid is extremely important in order to obtain a stable multilayer structure polymer, and generally the largest amount of catalyst is incorporated into each polymer layer. The use of a grafting cross-agent is essential for effectively synthesizing a two-layer elastic structure that is chemically bonded to the crosslinked elastic polymer (B') formed in the second stage. Without this graft bond, the two-layer elastomer structure would easily undergo phase destruction during melt molding, resulting in lower rubber efficiency and would not exhibit the desired excellent weather resistance, solvent resistance, water whitening resistance, etc. Innermost layer polymer (A′) in multilayer structure polymer []
The content of is 5 to 40% by weight, preferably 5 to 20% by weight, and is certified to be smaller than the content of the crosslinked elastic polymer (B'). Next, the crosslinked elastic polymer (B') is the main component that gives the multilayer structure polymer [] excellent flexibility.
It accounts for 30 to 80% by weight, preferably 35 to 60% by weight in the multilayer polymer. If the proportion of the crosslinked elastic polymer (B') is less than 30% by weight, sufficient flexibility will not be obtained, and if it exceeds 80% by weight, processability etc. will be significantly reduced, which is not preferable. As each component constituting the crosslinked elastic polymer (B'), the same components as those constituting the crosslinked elastic polymer (B) of the multilayer structure polymer [] described above are used. This is the same for the outermost layer polymer (C') and the intermediate layer (D') in the multilayer structure polymer [], and the outermost layer polymer (C) and the intermediate layer (D') of the multilayer structure polymer [] described above are the same. It consists of the same components as (D). It goes without saying that the lower the individual Tg of the crosslinked elastic polymer (B'), the more preferable it is, and particularly preferable physical properties can be obtained at -30°C or lower. Furthermore, in the case of the multilayer structure polymer [2], it is necessary that the two-layer crosslinked elastic body has a gel content of 85% or more and a swelling degree of 3 to 13, as determined by the method described above. Outermost layer polymer (C′) in multilayer structure polymer []
The content is 10% by weight or more and less than 50% by weight. The outermost layer polymer (C') also needs to have a single Tg of 60°C or higher, preferably 80°C or higher in order to obtain excellent solvent resistance and water whitening resistance. If the Tg of the polymer (C') alone is less than 60°C, satisfactory physical properties cannot be obtained. Each intermediate layer (D′) in the multilayer structure polymer []
The content is 5 to 35% by weight, preferably 5 to 25% by weight; if it is less than 5% by weight, it will not lose its function as an intermediate layer, and if it is more than 35 parts by weight, the balance of the final polymer will be disturbed. If the content of the entire intermediate layer exceeds 40% by weight, the overall balance will be lost, which is not preferable. The gel content of the final polymer of the multilayer structure polymer [] is preferably in the range of 60 to 95% by weight. If the gel content is less than 60% by weight, it will lead to a decrease in solvent resistance, and if it exceeds 95% by weight, it will lead to a decrease in moldability even when blended with a multilayer structure polymer [], which is not preferable. The above-mentioned multilayer structure polymers [] and [] can be obtained by a sequential multi-stage polymerization method using an emulsion polymerization method, but are not particularly limited thereto. It can also be obtained by an emulsion suspension polymerization method involving conversion. Further, there are no particular restrictions on emulsifiers, catalysts, and coagulants. The emulsion particle size of the multilayer structure polymer [] and [] final polymer is not particularly limited, but is 800 mm.
The most balanced structure is obtained in the range of ~2000 Å. The latex of these multilayered polymers is subjected to a salting-out treatment by adding additives such as antioxidants and lubricants, if necessary. Multilayer structure polymers [] and [] have similar polymer structures, and it is preferable from the viewpoint of transparency that only the ratio of each layer differs, but depending on the purpose, they can be obtained from completely different alkyl (meth)acrylates. It goes without saying that it is also possible to use objects. Multilayer structure polymer [] and multilayer structure polymer []
The blending ratio can be appropriately set within the range of 1 to 99 parts by weight/99 to 1 part by weight, preferably 10 to 90 parts by weight/90 to 10 parts by weight, depending on the purpose. For example, in cases where fluidity is particularly required, such as when molding into a film using the T-die method, the blending ratio of the multilayer structure polymer [ ] should be 50 parts by weight or less, preferably within the range of 10 to 40 parts by weight. It is desirable to keep it to a minimum. On the other hand, for applications that require extremely flexibility, it is natural to use a multilayer structure polymer [] of 50 parts by weight or more, preferably 50 to 50 parts by weight.
It is desirable to use it in a range of 90 parts by weight. Resin compositions containing 50 parts by weight or more of the multilayer polymer [] will certainly have lower fluidity than resin compositions containing 50 parts by weight or less of the multilayer polymer [], but they can be molded into thin films using a T-die. You should not experience any difficulty in molding unless you have to. Multilayer structure polymer [] and multilayer structure polymer []
The powders can be blended using a conventional method such as using a Henschel mixer, or they can be blended by mixing the respective latexes and then performing a treatment such as salting out. In addition, when blending the multilayer structure polymer [] and the multilayer structure polymer [], general additives such as ultraviolet absorbers, antioxidants, pigments, and lubricants can be added, and in particular, ultraviolet absorbers can be added. As a result, a resin composition with even better weather resistance can be obtained. In addition, at least one polymer selected from the group of polymers (i) or (ii) described above is added to 1 to 99 parts by weight of the resin composition containing the multilayer structure polymers of the present invention in the above proportions. A mixture of at least one kind of polymer selected from each group of (i) and (ii) is 99 to 1
Parts by weight can be blended. Multilayer structure polymer used in the present invention []
and [] is a crosslinked elastic polymer (B) containing an alkyl acrylate as a main component in the presence of an innermost layer polymer (A) or (A') containing a specific alkyl acrylate or alkyl methacrylate as a main component as described above.
or (B′) is polymerized, and the outermost layer is composed mainly of alkyl methacrylate and has a Tg of at least 60.
The outermost layer polymer (C) or (C') is placed at an intermediate layer (D) or (D') whose amount decreases monotonically from the polymer (B) or (B') layer to the polymer (C) or (C') layer; Each polymer layer other than the polymer (C) or (C') layer is effectively graft-bonded and has a multilayer polymer structure with a specific gel content, so it is considered that the refractive index is different. When blended with other thermoplastic resins with which it is compatible, it is possible to obtain a resin composition with excellent transparency and no or very little stress whitening. In particular, when blended with a methyl methacrylate resin, a resin composition with excellent transparency, stress whitening resistance, weather resistance, and impact resistance can be obtained. 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 polymers [ ] and [ ], and cannot be predicted from conventional methods of introducing rubber components. Also, vinyl chloride resin, polystyrene, AS resin,
When blended with polycarbonate resin,
The blend composition of the multilayer polymers [ ] and [ ] acts as a kind of weather resistance and impact resistance modifier, and brings about a significant improvement in weather resistance and impact resistance. Furthermore, blend compositions containing polyvinylidene fluoride have excellent properties such as weather resistance, transparency, stress whitening resistance, chemical resistance, toughness, and moldability. Blend composition of and multilayer structure polymer [] and []
A resin composition containing 50 to 99 parts by weight is 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 molded article, and has extremely high commercial value. The present invention will be specifically explained below using Examples. Note that "parts" and "%" in the examples are both "parts by weight" and "% by weight." Furthermore, the abbreviations used in the examples are as follows. MMA: Methyl methacrylate MA: Methyl acrylate BuA: Butyl acrylate 2EHA: 2-ethylhexyl acrylate St: Styrene BD: 1,3-butylene dimethacrylate AMA: Allyl methacrylate CHP: Cumene hydroperoxide SFS: Sodium formaldehyde sulfoxylate The Tg of each polymer layer used in the polymer layer can be calculated from the Tg value listed in the Polymer Handbook using the commonly known FOX formula: 1/Tg=α ₁ /Tg ₁ +α ₂ /Tg ₂ It is something that Example 1 (1) Production of multilayer polymer [] 250ml of ion-exchanged water was placed in a polymerization container equipped with a cooler.
Part, ester soda salt of sulfosuccinic acid 2
After adding 0.05 parts of SFS and stirring under nitrogen stream.
A mixture consisting of 1.6 parts MMA, 8 parts BuA, 0.4 parts BD, 0.1 part AMA and 0.04 parts CHP was charged. 70
After raising the temperature to ℃, the reaction was continued for 30 minutes to form the innermost layer polymer.
Polymerization of (A) was completed. Next, MMA 1.5 division,
A mixture of 22.5 parts of BuA, 1 part of BD, 0.25 parts of AMA, and 0.05% CHP to these monomer mixtures was added over 60 minutes and held for an additional 60 minutes to form the polymer (A), A two-layer crosslinked elastic body consisting of two layers (B) was polymerized. The degree of swelling of the two-layer crosslinked elastic body thus obtained in MEK was 10.0.
Gel content was 90%. Next is MMA5, which corresponds to the middle class (D), and BuA5.
0.1 parts of MMA was added over 10 minutes for polymerization, and finally 52.25 parts of MMA,
A mixture of 2.75 parts of BuA was similarly polymerized to obtain an outermost layer polymer (C) and a multilayer structure polymer [-(1)]. However, when polymerizing the middle layer (D) and the outermost layer (C), it corresponds to 0.1% of the amount of monomer used in each layer.
CHP was used. Similarly, multilayer polymers [−(2)] to [
-(5)], comparative polymers (1), (2), and (3) were polymerized. In all cases, the final particle diameter was 1000 to 1500 Å. These polymer latexes were salted out in a conventional manner, washed, dehydrated, and dried to obtain dry powder. Their compositions and physical properties are shown in Table 1. (2) Production of multilayer structure polymer [] The table was prepared in exactly the same manner as in the production of multilayer structure polymer [] in (1) above, except that the crosslinked elastic polymer (B') was added for 90 minutes. Multilayer structure polymer having the polymer structure shown in 2 [-(1)] ~
[-(5)] and comparative polymer (4) were polymerized. The final particle size of these polymers is 1000
It was in the range of ~1500 Å. These polymer latexes were also salted out in a conventional manner, washed, dehydrated, and dried to obtain dry powder. Their compositions and physical properties are shown in Table 2.

【table】

【table】

[Table] (3) Preparation and evaluation of resin composition Multilayer structure polymers [-(1)] and [-(1)] were blended in the proportions shown in Table 3, and 2 parts of ultraviolet absorber (trade name Tinuvin-P (manufactured by Ciba Geigy) was added, mixed well, and pelletized using an extruder. After drying the obtained pellets at 70°C for a day and night, a molding processability test was conducted using an injection molding machine. The results are also shown in Table 3. The criteria for determining moldability are as follows. <Moldability evaluation criteria> 〇: Can be easily molded with an injection molding machine. △: Barely possible to mold with an injection molding machine. ×: Difficult to mold with an injection molding machine. Further, the same pellets were molded into a sheet with a thickness of 250 μm by the T-die method. For the samples that could be molded into good sheets, the transparency (total light transmittance and haze value) was evaluated based on JIS K 6714, and the tensile modulus was measured as a measure of flexibility. For samples from which a good sheet could not be obtained, the tensile modulus was not measured, and the transparency was evaluated by visual judgment. These results are also shown in Table 3. In addition, for well-formed sheets, a 3,000-hour accelerated exposure test is conducted using a Sunshine Weather-Ometer, and the tensile elongation at break is measured before and after the test to determine the elongation retention at break, which is a guideline for weather resistance. And so. These measurement results are also shown in Table 3. Also, multilayer structure polymer [-(1)] ~
[-(5)], [-(1)] to [-(5)] and comparative polymers (1) to (4) were blended in the proportions shown in Table 4,
A similar evaluation was conducted. The evaluation results are shown in Table 4. All of the products of the present invention have excellent transparency and weather resistance, and have appropriate flexibility and workability. Note that ratios (1) to (4) in Table 4 are for comparative polymer (1)
~ Comparative polymer (4) is shown.

【table】

[Table] Example 2 Multilayer structure polymer synthesized in Example 1 [-(1)]
50 parts of a resin composition (inventive example (2)) consisting of 70 parts of multilayer structure polymer [-(1)] and 30 parts of multilayer structure polymer [-(1)] were mixed with MMA/MA copolymer (MMA/MA=99/1 weight ratio, ηSP). /C
= 0.60 (measured as a solution with a concentration of 0.10 g/d)) was blended with 50 parts using a Henschel mixer, and then pelletized using an extruder. The obtained pellets were dried at 80℃ for a day and night, and T-
A 0.5 mm thick sheet was formed using a die. This blended polymer has good sheet formability;
A sheet with excellent transparency, gloss, etc. was obtained. Furthermore, using the same pellets, an injection molded plate with a thickness of 2 mm was obtained without injection molding. The total light transmittance and in-situ impact strength of the obtained molded plate were measured. The total wire transparency was 93%, and the in-situ impact strength was 35 kg·cm/cm ² , both showing extremely good values. Further, the above-mentioned molded plate was subjected to an accelerated exposure test for 3000 hours using a Sunshine Weather-Ometer, and the gloss retention rate was measured. Gloss retention rate is 94
%, indicating that the product of the present invention also has excellent weather resistance. Example 3 Multilayer structure polymer synthesized in Example 1 [-(1)]
60 parts of the multilayer structure polymer [-(1)] and 10 parts of polyvinylidene fluoride (trade name Kynar 500, manufactured by Pennwalt) were blended using a Henschel mixer, and then pelletized using a screw extruder.
The obtained pellets were formed into a film with a thickness of 80 μm by the inflation method. The tensile strength and elongation (JIS Z
170-2), haze value (ASTM-D 1003-
61) was measured. Tensile modulus 8×10 ³ Kg/
cm ² , breaking strength 340Kg/cm ² , breaking elongation 200%, haze value
Both values showed extremely good values of 4.8%. In addition, the obtained film was bonded to a galvanized 0.5 mm cold-rolled steel plate using an adhesive, and this bonded sample was subjected to a Dupont impact test (tip R = 1/2 inch,
The test was carried out at a load of 1 kg, a drop height of 50 cm, and a temperature of 20°C). The impacted area did not show any whitening and no cracks were observed. Further, the film was subjected to an accelerated exposure test for 3000 hours using a Sunshine Weatherometer, and the tensile strength and elongation of the exposed sample was measured. Tensile elongation retention rate of sample after exposure (elongation of unexposed product is 100
The value when expressed as %; a measure of weather resistance) is 90%
This showed that the product of the present invention also has excellent weather resistance.

Claims (1)

[Scope of Claims] 1. A thermoplastic resin composition comprising 1 to 99 parts by weight of at least one of the following multilayer structure polymers [] and 99 to 1 part by weight of at least one of the following multilayer structure polymers []. Multilayer structure polymer []: 80 to 100 parts by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (A ₁ ), 0 to 20 parts by weight of a copolymer A monomer having a polymerizable double bond (A ₂ ), 0 to 10 parts by weight of a polyfunctional monomer (A ₃ ), based on 100 parts by weight of the total amount of (A ₁ ) to (A ₃ ) 0.1
The composition consists of ~5 parts by weight of a graft cross-agent, which accounts for 5-35% by weight of the innermost layer polymer (A) in the multilayer structure polymer, and 80-100 parts by weight of a carbon number of 1-8. Alkyl acrylate having an alkyl group (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 ) , 0.1 per 100 parts by weight of the total amount of (B ₁ ) to (B ₃ )
A crosslinked elastic polymer (B) consisting of ~5 parts by weight of a grafting agent and having a proportion of 10 to 40% by weight in the multilayer polymer [], 51 to 100 parts by weight of a carbon number of 1 to 4 alkyl methacrylate (C ₁ ), 0 to 49 parts by weight of a monomer (C ₂ ) having a copolymerizable double bond, and has a Tg of at least 60°C, The outermost layer polymer (C), which accounts for 50 to 80% by weight, is the basic structural unit, and 10 to 90 parts by weight of the intermediate layer (D) is formed between the polymer (B) layer and the polymer (C) layer. Alkyl acrylate (D ₁ ) having an alkyl group having 1 to 8 carbon atoms, 90 to 10 parts by weight of an alkyl methacrylate (D ₂ ) having an alkyl group having 1 to 4 carbon atoms, 0 to 20 parts by weight of a copolymerizable Monomer having a double bond (D ₃ ), 0 to 10 parts by weight of polyfunctional monomer (D ₄ ), and 0.1 to 100 parts by weight of the total amount of (D ₁ ) to (D ₄ ).
An intermediate layer (D) consisting of a composition of ~5 parts by weight of a graft cross-agent, in which the amount of alkyl acrylate in the intermediate layer (D) monotonically decreases from the crosslinked elastic polymer (B) to the outermost layer polymer (C). ), and the gel content of the multilayer polymer is at least 50%. Multilayer structure polymer []: 80 to 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (A ₁ '), 0 to 20 parts by weight of co-monomer. Monomer having a polymerizable double bond (A ₂ ′), 0 to 10 parts by weight of a polyfunctional monomer (A ₃ ′), total amount of (A ₁ ′) to (A ₃ ′) 100 0.1 per part by weight
Innermost layer polymer (A') consisting of ~5 parts by weight of a graft cross-agent and occupying a proportion of 5 to 40% by weight in the multilayer structure polymer [], 80 to 100 parts by weight of a carbon number of 1 to 100%; Alkyl acrylate (B ₁ ′) having 8 alkyl groups, 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 0.1 per 100 parts by weight of the total amount of (B ₃ ′), (B ₁ ′) to (B ₃ ′)
A crosslinked elastic polymer (B') consisting of ~5 parts by weight of a grafting agent and having a proportion of 30 to 80% by weight in the multilayer polymer [], 51 to 100 parts by weight of a carbon number of 1 to _A multilayered _polymer [ ] The outermost layer polymer (C′), which accounts for 10% by weight or more and less than 50% by weight, is the basic structural unit, and an intermediate layer (D) is formed between the polymer (B′) layer and the polymer (C′) layer. 10 to 90 parts by weight of an alkyl acrylate having an alkyl group of 1 to 8 carbon atoms (D ₁ ′), 90 to 10 parts by weight of an alkyl methacrylate having an alkyl group of 1 to 4 carbon atoms (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 ′), (D ₁ ′) to ( D ₄ ′) 0.1 per 100 parts by weight
The intermediate layer (D') has a composition of ~5 parts by weight of a grafting agent, and the amount of alkyl acrylate in the intermediate layer (D') decreases monotonically from the crosslinked elastic polymer (B') to the outermost layer polymer (C'). A multilayer structure polymer having at least one layer (D'). 2 Resin blend 1 consisting of 1 to 99 parts by weight of at least one of the following multilayer structure polymers [] and 99 to 1 parts by weight of at least one of the following multilayer structure polymers []
~99 parts by weight of at least one polymer selected from the following groups (i) or (ii), or a mixture of at least one polymer selected from each of the groups (i) and (ii).
A thermoplastic resin composition containing ~1 part by weight. Multilayer structure polymer []: 80 to 100 parts by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (A ₁ ), 0 to 20 parts by weight of a copolymer A monomer having a polymerizable double bond (A ₂ ), 0 to 10 parts by weight of a polyfunctional monomer (A ₃ ), based on 100 parts by weight of the total amount of (A ₁ ) to (A ₃ ) 0.1
The composition consists of ~5 parts by weight of a graft cross-agent, which accounts for 5-35% by weight of the innermost layer polymer (A) in the multilayer structure polymer, and 80-100 parts by weight of a carbon number of 1-8. Alkyl acrylate having an alkyl group (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 ) , 0.1 per 100 parts by weight of the total amount of (B ₁ ) to (B ₃ )
A crosslinked elastic polymer (B) consisting of ~5 parts by weight of a grafting agent and having a proportion of 10 to 40% by weight in the multilayer polymer [], 51 to 100 parts by weight of a carbon number of 1 to 4 alkyl methacrylate (C ₁ ), 0 to 49 parts by weight of a monomer (C ₂ ) having a copolymerizable double bond, and has a Tg of at least 60°C, The outermost layer polymer (C), which accounts for 50 to 80% by weight, is the basic structural unit, and 10 to 90 parts by weight of the intermediate layer (D) is formed between the polymer (B) layer and the polymer (C) layer. Alkyl acrylate (D ₁ ) having an alkyl group having 1 to 8 carbon atoms, 90 to 10 parts by weight of an alkyl methacrylate (D ₂ ) having an alkyl group having 1 to 4 carbon atoms, 0 to 20 parts by weight of a copolymerizable Monomer having a double bond (D ₃ ), 0 to 10 parts by weight of polyfunctional monomer (D ₄ ), and 0.1 to 100 parts by weight of the total amount of (D ₁ ) to (D ₄ ).
An intermediate layer (D) consisting of a composition of ~5 parts by weight of a graft cross-agent, in which the amount of alkyl acrylate in the intermediate layer (D) monotonically decreases from the crosslinked elastic polymer (B) to the outermost layer polymer (C). ), and the gel content of the multilayer polymer is at least 50%. Multilayer structure polymer []: 80 to 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms or alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms (A ₁ '), 0 to 20 parts by weight Monomer having a copolymerizable double bond (A ₂ ′), 0 to 10 parts by weight of polyfunctional monomer (A ₃ ′), total amount of (A ₁ ′) to (A ₃ ′) 0.1 per 100 parts by weight
Innermost layer polymer (A') consisting of ~5 parts by weight of a graft cross-agent and occupying a proportion of 5 to 40% by weight in the multilayer structure polymer [], 80 to 100 parts by weight of a carbon number of 1 to 100%; Alkyl acrylate (B ₁ ′) having 8 alkyl groups, 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 0.1 per 100 parts by weight of the total amount of (B ₃ ′), (B ₁ ′) to (B ₃ ′)
A crosslinked elastic polymer (B') consisting of ~5 parts by weight of a grafting agent and having a proportion of 30 to 80% by weight in the multilayer polymer [], 51 to 100 parts by weight of a carbon number of 1 to _A multilayered _polymer [ ] The outermost layer polymer (C′), which accounts for 10% by weight or more and less than 50% by weight, is the basic structural unit, and an intermediate layer (D) is formed between the polymer (B′) layer and the polymer (C′) layer. 10 to 90 parts by weight of an alkyl acrylate having an alkyl group of 1 to 8 carbon atoms (D ₁ ′), 90 to 10 parts by weight of an alkyl methacrylate having an alkyl group of 1 to 4 carbon atoms (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 ′), (D ₁ ′) to ( D ₄ ′) 0.1 per 100 parts by weight
The intermediate layer (D') has a composition of ~5 parts by weight of a grafting agent, and the amount of alkyl acrylate in the intermediate layer (D') decreases monotonically from the crosslinked elastic polymer (B') to the outermost layer polymer (C'). A multilayer structure polymer having at least one layer (D'). Polymer (i): A homopolymer of a monomer having the following general formula (a), (b) or (c) or a copolymer consisting of two or more of these monomers. CH ₂ = CXY ... (a) However, in the formula, X and Y are H, Cl, F, Br, CH ₃ ,
It is either COOH, COOCH ₃ , CN, OCOCH ₃ , C ₆ H ₅ , an alkoxy group, OCCH ₃ or SO ₃ H. CF ₂ =CFZ...(b) However, Z in the formula is either H, F, Cl, or CF ₃ . However, in the formula, R is a fluoroalkyl group. Polymer (ii): polycarbonate, thermoplastic polyester, polyamide.