JPS58215444A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic acrylic resin compsn. having excellent transparency, resistance to stress-whitening, processability, etc., by blending specified two kinds of multi-layer structure polymers. CONSTITUTION:A multi-layer structure polymer ( I ) composed of a crosslinked elastomeric polymer layer (inner layer) mainly composed of an alkyl acrylate, a resin layer (outer layer) having a Tg of 60 deg.C or above mainly composed of an alkyl methacrylate and an intermediate layer therebetween mainly composed of an alkyl acrylate and an alkyl methacrylate, is blended with a multi-layer structure polymer (II), in which the basic polymer structure is the same as that of the polymer ( I ), but the amount of the crosslinked elastomeric polymer is equal to or larger than that of the resin layer, in a weight ratio of 1-99:99-1, the amount of the alkyl acrylate in the intermediate layer being reduced from the inner layer toward the outer layer.

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, the crosslinked elastic polymer layer (inner layer) has a two-layer structure and the glass transition temperature (hereinafter abbreviated as Tg) is 60.
It has a special Chibird structure between the resin layer (outer layer) and the resin layer (outer layer), and the resin layer (2) has transparency, 1i11 weatherability, *1M machinability, 1 stress whitening resistance.

The basic poly-E structure A is the same as the multilayer structure polymer CD, but the resin layer has the same or higher crosslinking elasticity 1.
Transparent and highly flexible multilayer structure having 1 combined layer 1) A transparent and highly flexible multilayer structure obtained from r2-Sir blended with at least one of 1) combined layer and 1) combined layer, and -1 weatherability, solvent resistance, and Stress whitening +! 1. The present invention relates to a novel acrylic thermoplastic resin composition that is superior to 1" r+ collar.

Acrylic resins, especially methyl methacrylate polymers, are known to have both excellent transparency and weather resistance, and are used in cast molded products.

Widely used for extrusion molded products. However, these methyl methacrylate polymers are generally 4II
It is widely known that it is unsuitable for films and sheets because it is brittle, and that it cannot be used for applications that require flexibility. .

(5) 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 as a result, the weather resistance has been significantly reduced. However, it is possible to improve toughness and flexibility without sacrificing the excellent features of methyl methacrylate polymers, such as transparency and weatherability. Attempts to grant it have not been successful.

Furthermore, from the viewpoint of materials for film sheets, several methyl methacrylate-based multilayer polymers containing acrylic rubber have been proposed.

However, even in these multilayer structure polymers, toughness,
In most cases, the inherent characteristics of methyl methacrylate polymers, such as transparency and weather resistance, are sacrificed in order to impart flexibility, which is not satisfactory. Furthermore, these multilayered polymers have flexibility and a property that is processable (fluidity) due to constraints on the polymer structure.

Since this property (4) is contradictory to various properties such as weather resistance and solvent resistance, there is a limit to how much flexibility can be added without sacrificing these 11/1 qualities. For this reason, it is difficult to handle it as a film/sheet vehicle.Although it is possible to provide bundle flexibility and toughness of 1 m, it cannot be used for applications that require greater flexibility. The current situation is 1).

In view of the current situation where the inventors are
Weather resistance, stress whitening resistance without sacrificing twA, *l solvent? 1V (excellent, arbitrary flexibility, 1st birch acrylic yarn 1 unite)
In addition, acrylic acrylate with a two-layer structure,
Cross-linked elastic polymer wI (within 1 m) such as 6)
and '[' Alkyl methacrylate with g of 60°C or higher - 1%
-, a resin layer (1 m) with (1 m) as a component (a middle layer between /J with alkyl acrylate and alkyl methacrylate as the main components, and the number of alkyl acrylate monotonically decreases from the crosslinked elastic 1 combined layer to the resin layer) - has a basic polymer structure containing at least one layer of -, and the resin layer is transparent, weather resistant, solvent resistant, and stress whitening resistant, such that the resin layer has a superior amount to the crosslinked elastic piIt1 body layer (b); At least one type of multilayer structure polymer CD with excellent processability etc. The basic polymer structure is the same as multilayer structure polymer [I], but it contains a crosslinked elastic polymer layer in an amount approximately equal to or greater than that of the resin layer. The present invention was accomplished by discovering that the object of the present invention can be achieved by blending at least one type of transparent and particularly flexible multilayer polymer [■].

The gist of the present invention is to provide a first thermoplastic resin composition comprising 1 to 99 parts by weight of at least one kind of multilayer structure polymer [I] and 99 to 1 part by weight of at least one kind of multilayer structure polymer [■]. invention and multilayer structure polymer CD (2) 1 to 99 parts by weight of at least one kind and multilayer structure polymer [11]
1 to 99 parts by weight of a resin blend consisting of 99 to 1 parts by weight of at least one of the following, and at least one kind of polymer selected from the following group (1) or (11), or (1) and (11).
The second invention is a thermoplastic (6) plastic resin composition comprising 99 to 1 part by weight of a mixture of at least one type of polymer selected from each group.

Polymer (1): A homopolymer of monomers having the following general formula (a), (++) parent #J (0) or a copolymer consisting of two or more of these monomers.

OH2w OX Y e m 11 @
II (a) However, in the formula, X, Yiil(,01,F,Br
, ons.

000H, OOOOHm, (IN, Ofi+
00H,,0sHs, alkoxy group, 0OOH1
It is either 1,80sH.

OF2-01' Z @ @ II @
11 (1)) However, 2 in the formula is H, 11', (31,
,OF,.

0112=000()i(ee**++ (c) bite Oll.

However, in the formula, R is a fluoroalkyl group.

Polymer (ij): Polycarbonate, thermal 1IWIi polyester.

polyamide.

In addition, in the present invention, the multilayer structure polymer [1) and the multilayer structure 1 combination 11 it] and the pot have the polymer structure (7) described in (7).

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 (Al) having an alkyl group having 1 to 4 carbon atoms.

0 to 20 parts by weight of a monomer having a copolymerizable double bond (AD9) 0 to 10 parts by weight of a polyfunctional monomer (A3).

(4) to 100 parts by weight of the total amount of (A3) [11 to
The innermost layer polymer (A) is composed of 5 parts by weight of the graft cross-agent, and the proportion in the multilayer structure polymer [■] is 5 to 35 parts by weight.

80 to 100 parts by weight of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms (B+).

A monomer (Ba) having a copolymerizable double bond in an amount of 0 to 201 J parts.

0 to 10 M parts of polyfunctional monomer (B3).

For a total of 1100 parts by weight of (Bl) to (B3), [1,
(8) The proportion of the grafting agent in the multilayer structure polymer [1] is 10 to 40 parts by weight.
One of the most popular materials is the polymer (B).

51-100 violet alkyl methacrylate-1 ((++) having 1-4 carbon atoms.

0 to 49 parts by weight of a monomer having a double bond capable of co-merging (Off) Tg is at least 60°C, and the proportion of 1c in the multilayer structure polymer [1] is 50-80 weight-
S outer layer summation (0).

The basic structural unit and [2.1 combined CB] layer and polymer (0)
An alkyl acrylate (D+) having 10 to 90 parts by weight of an alkyl group having 1 to 8 carbon atoms as an intermediate layer (D) between the layers.

90 to 10 parts by weight CO alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms.

A monomer having 0 to 201 Jt parts of copolymerizable double bonds (Raven).

0 to 10 weight 1 part polyfunctional t'1g mono-iris (D4).

a for 1111ooW1 part of (Dl) to (D4)
1 to 5 parts by weight of Kraft crossover 1 (D composition), medium (9) The amount of alkyl acrylate in the interlayer (D) is monotonous from the crosslinked elastic polymer (B) to the outermost layer polymer (C) A multilayer structure polymer [1], which has at least one intermediate layer (D) such that the gel content decreases, and the gel content of the multilayer structure polymer is at least 50%.

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 (AD).

0 to 20 parts by weight of a monomer (A2') having a copolymerizable double bond.

0 to 10 parts by weight of polyfunctional monomer (3 A).

(AI') ~ (A1 to 5 parts by weight of the grafting agent based on the total amount of 100 parts by weight of the three A), υ, the proportion of which in the multilayer structure polymer [I[] is 5 to 40 parts by weight. The innermost layer polymer (A) is

Alkyl acrylate having 80 to 100 parts by weight of an alkyl group having 1 to 8 carbon atoms (B1'9゜monomer (8') having 0 to 20 parts by weight of a (10) copolymerizable double bond) .

0 to 10'll11 parts of polyfunctional P [monomer (Bs')
.

(1 set of B ~ (Agency) 11 [10111 copies [L]
Depending on the composition of the graft cross-agent of 1 to 5 parts by weight, the crosslinked elastic polymer (B) accounts for 30 to 80 parts by weight of the multilayer structure polymer [■].

51-100] [-translation of the position part singular 1-4 alkyl methacrylate-) (0+').

Copolymerization of 0 to 49 double lid portions t = monomer (0 □') having a J-capable double bond. Accounting for 10% or more by weight50
10 to 9011r parts of carbon P11 as IIk114F layer polymer (C is the basic structural unit and 12, polymer (B') layer and polymer (0 intermediate layer between C layers)') Alkyl acrylate having ~8 alkyl groups) (DI').

90-10] Alkyl methacrylate () having an alkyl group of carbons #91-4 in the i1i part.

It has a double bond for both 11 and 0 to 2011ii parts (
11) Monomer (Da).

0 to 10 parts by weight of polyfunctional monomer (4 Bs.

(Dl ~ (11 parts per 100 parts by weight of the total amount of 4 B)
9. The intermediate layer (
A multilayer structure polymer having at least one intermediate layer (D') in which the amount of D alkyl acrylate monotonically decreases from the B to the outermost layer polymer (C).
111゜The features of the present invention are transparency and weather resistance.

A multilayer polymer with excellent stress whitening resistance, solvent resistance, and processability], and although its processability is slightly inferior, it is extremely flexible and transparent.

Multilayer structure polymer CI with excellent weather resistance and stress whitening resistance
By incorporating O, transparency and weather resistance that could not be obtained with conventional multilayer polymers alone can be achieved.

This is because the thermoplastic resin composition has excellent flexibility and processability.

The multilayer structure polymer [Kawa] and the multilayer structure polymer [Kawa] have the same basic polymer structure, and both have the following characteristics. That is, (12) (1) The cross-linked elastic oil FT body (13 is a two-layer elastic body structure containing the innermost layer polymers (A) and (M') as inner layers, respectively; (2) ) Outermost layer polymer which is a resin layer (pTg is set at 60°C or higher; (3) Between crosslinked elastic polymer j- and #ll/'% layer polymer layer from crosslinked elastic polymer layer to outermost layer polymer At least one layer of intermediate W4 is arranged in such a manner that the ratio of alkyl acrylate monotonically decreases toward the layer; (4) chemical grafting is carried out between each of the above layers using a grafting agent; ( 51Ji polymer gel containing 411 was made to be at least 50 grams.

and h et al.'s fl-'), the multilayer structure 1 combination ('1] and [■] is transparent and weather resistant.

In addition to the basic properties of the multilayer structure 1 composite composition used in the present invention, such as excellent anti-scratch/whitening properties and -1 solvent properties, -C can be satisfied. If you lack it, you won't get what you should be satisfied with. In particular, the multilayer structure polymer CII and [ID
is characterized in that the crosslinked elastic polymer layer is composed of a two-layer elastic structure including an innermost polymer layer 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, in order to provide the above-mentioned properties of solvent resistance and water whitening resistance while maintaining excellent weather resistance, there is a limit to the elastic body structure consisting of only one layer obtained by conventional one-stage polymerization. .

Multilayer structure polymer used in the present invention [ID and [
■] is a crosslinked elastic polymer (
The innermost layer polymers (A) and (A) are present in the cores of B) and (B, respectively, and the presence of the innermost layer polymers (A) and (A) causes crosslinking when stress is applied. The elastic polymers CB) and (B) polydispersively relax the stress concentrated in the two layers14), and as a result, the incidence of microvoids increases, resulting in excellent impact resistance even without apparent soil stress whitening1. In the case of the 1.4° multilayer structure A 1$1 base [1,], the ratio of the resin layer is set higher than the crosslinked elastic polymer layer, so the flexibility is slightly lower. Although it is lacking, the weather resistance, solvent resistance, etc. are even better, and Jll
By suppressing the gel content of the IAI1 combination to 80 or less, it is said to have excellent processability.

Alkyl acrylate having an A-A-kyl group having 1 to B carbon atoms and constituting the inner layer polymer (A) of the multilayer structure polymer [I]
hFi may be linear or branched, and may be methyl acrylate-1, ethyl acrylate, propyl'I acrylate-1, butyl acrylate, 2-ethylhexyl acrylate), n-octyl acrylate, etc. These can be used alone or in combination, but those with a low Tg are more preferred.

In addition, alkyl methacrylate-1r having an alkyl group having 1 to 4 carbon atoms, i1-chain 1-branched form (15) may be used, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. may be used alone or Used in combination. These alkyl (meth)acrylates (A is used in the range of 80 to 100 parts.Also, it is most preferable that these alkyl (meth)acrylates are used uniformly in all multi-stage layers, but depending on the final purpose, υ in which more than one type of monomer is mixed, or a different type of (meth)acrylate may be used.

In addition, monomers with copolymerizable double bonds (lower alkyl acrylate, lower alkyl diacrylate, cyanethyl 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, within a range not exceeding 20% by weight in component (A),
Methacrylate trile and the like can be used.

Furthermore, polyfunctional monopolymers (alkylene glycol dimethacrylates such as ethylene glyco(16)-dimethacrylate), 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate are preferred. Preferably, divinylbenzene, trivinylbenzene, volivylbenzene, and alkylene glycol diacrylate isoelectrics can be used. These monomers are effective in bridging the layer in which they are contained, but do not act in bonding layers with other layers. , polyfunctional monomer (A0) Even if it is not used at all, as long as the grafting agent is present, it will be stable. 1rb of multi-layered cypress wood can be used, but depending on the required physical properties, 1 arbitrary VC can be used, but the amount used Fio ~10'M parts.

On the other hand, the graft cross-agent is J'Lt, which is an allyl, methallyl or crotyl ester of a copolymerizable α,β-unsaturated carboxylic acid or dicarboxylic acid, preferably an allyl ester of acrylic acid, methacrylic powder, maleic acid or fumaric acid.
% allylmeth (1/) acrylate has excellent effects. 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 effectively works 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 1 and the above component (4)
The total amount of (A3) is used in the range of α1 to 5 parts by weight, preferably Fiα5 to 27Jj parts, per 100 heavy lid parts. If the amount used is less than 1 part by weight, the effective amount of graft bonding will be small and the bonding between the layers will be insufficient. 51 again! If the amount used exceeds 1 part of IR, the amount of reaction with the crosslinked elastic polymer (B) polymerized in the second stage will be large. This causes a decrease in the elasticity of the elastic body.

(18) Combine the innermost layer + A) t, J graph: 7 active layers,
The Tgt and 1# are appropriately set according to the required physical properties of the mounting body. Further, the crosslinking density is generally the same as that of the crosslinked elasticity 1 coalescence ()3), or even higher, which is advantageous in terms of quality. It is possible that the innermost layer polymer (A) and the crosslinked elastic polymer (13) have the same composition, but at one time (1
4. It is not included, but it is based on the convenience of the second stage. It is a military expense to have a more elastic structure, and the catalyst 1. Setting the crosslinking density, etc. r, I if it is advantageous that the coalescence (A) is higher.

In the initial polymerization, the innermost layer polymer (A
) is extremely important in order to obtain a stable l-6, multi-j structure offshore body, and is generally present in the largest amount in each polymer layer.

Use 1 of the graft cross-linking agent is the cross-linking bullet V formed at the second fork.
1. ．． ) Two-layer elastic body structure chemically bonded between 11 (+, (13) and q) 1. +I effect k (1,□＠This is essential for forming the structure) ・Without bonding, two-layer elastic body structure purpose Mlll 37v, phase destruction easily occurs during forming (1v) Same rubber efficiency Not only does it deteriorate, but it also becomes difficult to exhibit the desired excellent weather resistance, stress whitening resistance, etc.

The content of the innermost electropolymer (A) in the multilayer structure polymer [1] is 5 to 55 times-1, preferably 5 to 15 times, and lower than the content of the crosslinked elastic polymer CB). is preferred.

Next, the crosslinked elastic polymer (
B) is the main component that gives rubber elasticity to the polymer CD, and contains 80 to 100iii parts of carbonate (B+), 0 to
20 parts by weight of a monomer having a copolymerizable double bond ((
A1 to 5 polyfunctional monomers (B3) and (13+) to (100 parts by weight of the total powder)
It consists of 1 part grafting agent.

Alkyl acrylate having an alkyl group having 1 to 8 carbon atoms
) As CB+), the alkyl acrylates exemplified in (A1) above can be used alone or in combination;
A low g value is preferable.

(20) Monomer with double bond f31 capable of copolymerization (B2)
The most preferred is lower alkyl methacrylate, and the same monomers as in Example 7 J<L ft are used. , also as a craft cross-agent -t Jl I"4
For the first inner J-weight body (mu), 76 and q) are used as an example.

The Tg of the crosslinked elasticity 1 combination (II) alone is 0°C or lower, preferably 1 (~611°C or higher), giving good physical properties.

Multilayer structure'111iu body [Crosslinked elastic polymer CB in 11
The content of )'' is preferably in the range of 10 to 40 times, and is preferably higher than the content of the innermost layer polymer (A).

In this way, the innermost layer polymer (MU) and the crosslinked elastic polymer CB)
Because it is a two-layer cross-linked elastic material consisting of a two-layer elastic structure in which the rubber is grafted and bonded, it has become possible to simultaneously satisfy various properties that could not be achieved with conventional mono-based rubbers. It is something.

It should be noted that this more elastic body has excellent physical properties when the gel content of 4411 determined by the following measurement method is set to 85 cm or more, and the swelling carbon is set in the range of 5 to 13 degrees. ) is necessary to obtain.

(Measurement method for gel content and Ml moisture content) A predetermined amount of the two-layer crosslinked elastic material was sampled according to JIS K-6588, and methyl ethyl ketone (hereinafter referred to as M
Abbreviated as KK. ), immerse it in water to swell, pull it up, wipe off the attached MFiK, measure its weight, then dry and remove MBK in a vacuum dryer, read the absolute dry weight that has become constant, and calculate it using the 9th equation. do.

Generally, if the degree of polymerization of the crosslinked elastic polymer (B) is as high as possible, high impact strength will be imparted to the final polymer. On the other hand, for the innermost layer polymer (A) that interacts with the core, this is not the case; rather, a large amount of catalyst was used for the stability of the initial polymerization including particle formation, and the graft active groups were also used in a polyphonic manner. Monoga2 (22) Layered crosslinked elastic material and [2] have good performance.

Furthermore, the outermost layer polymer (0) constituting the multilayer 411 trivial [1] is a material that distributes moldability, mechanical properties, etc. to the multilayer body [1], and constitutes Do<
(11) The alkyl methacrylate L/-1 exemplified in the component 1^(; mentioned 1.6 (Mu1) component is also (C2
) component j7 is a lower alkyl acrylate or the above-mentioned it (kJ hv, ri), and the monomers exemplified in 1. are used alone or in combination.

The '(0 凰) component has a range of 51 to 11111 parts, and the (02) component has a range of θ to 491 ili parts.

In addition, in order to obtain excellent physical properties, the Tg Id of the 91st layer*@body (0) is preferably 80°C.
It is necessary that it is above. 1 of the polymer (0) alone
When the temperature is less than 60°C, even if the final polymer CD has a gel content of 50°C or more, it will not have excellent physical properties.

Containment of jl outer layer polymer (0) in multilayer structure polymer [1] -1dtj, 50-1301kfi Excellent T#+le.

The multilayer structure polymer [1] for VC toilets of the present invention [1] is the above-mentioned (2)
3) The innermost layer polymer (A), the crosslinked elastic polymer (B) and the outermost layer polymer (C) are used as basic structural units, and further the single polymer (B
) layer and the polymer (0) layer is 10 to 90'j! Alkyl acrylate having an alkyl group having 1 to 8 carbon atoms in the J portion
) (Dll, 90 to 10 molar parts of alkyl methacrylate (D2) having an alkyl group having 1 to 4 carbon atoms, 0 to 2
The intermediate layer ('D) composed of 0 parts by weight of the copolymerizable material is such that the amount of alkyl acrylate in the intermediate layer (D) is the same as that of the polymer ('D).
At least one layer is arranged so as to monotonically decrease from layer B to the polymer (0) layer. Here, the components (Dl) to (D4) and the grafting agent are each (
Bt), (Ct), (A2), (powder and inner layer polymer (same as the graft cross-agent used in kJ). The graft cross-agent used in the intermediate layer (D) is This is essential for tightly bonding the combined layers and obtaining excellent physical properties.

(24) Content of each intermediate layer (D) in the multilayer structure polymer [1]
i115-3511N11, preferably 5-25 cars II
If it is less than 5'II-1, it will not lose its function as an intermediate layer, and if it exceeds 1r55 ILiT, the balance of the outermost layer polymer will be undesirable.

Furthermore, the multilayered polymer used in the present invention has a gel content of at least 50 grams, preferably at least 60 grams, which, together with the above-mentioned special structure, makes it highly resistant to ship stress whitening.

□ Provides superior properties such as impact resistance, solvent resistance, and water whitening resistance. In this case, q) gel content includes the two-layer crosslinked elastic body itself and the graft components of the crosslinked elastic body-1 of the intermediate layer (D) and outermost layer polymer (0), and Unique roofing is a single layer IlqbMI [lK] of multilayer structure polymer [1].
MM & embroidery 12. Leave overnight at 25°C (This is the weight gain of insoluble matter after centrifugation for 90 minutes at 16,000 r, p, m in a centrifuge. JIQ of gel content.
The weight is the weight of the two-layer crosslinked elastic body, the graph L-chain, and the O added weight, which can also be replaced by the grafting rate, but in the present invention (25), since the polymer [1] has a special structure, it contains gel. The amount was used as a guideline for the amount of grafting.

From the point of view of solvent resistance, a gel-containing lid is more advantageous, 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 80 qb.
degree is preferred.

On the other hand, the basic polymer structure of the multilayer structure polymer Ell is the same as that of the multilayer structure polymer CD, 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 [1], the amount of free polymer is lower, so the processability is slightly lowered, but the flexibility is extremely excellent. In addition, since it has the above-mentioned structural features of the polymer, it maintains transparency and weather resistance even when the crosslinked elastomer component increases.

-1 Properties such as stress whitening properties hardly deteriorate with #1.

Each component (mu 1') 1 (A 2, (A3') and graft (26) constituting the innermost layer polymer (A') of the multilayer structure polymer [n], each of the cross-agents has the above-mentioned group 1-structure Each component (At) constituting the innermost layer polymer (^) 1 of the polymer [■].

(Mz), (Ai) and the same graft cross-agents are used.

Multilayer structure 11 coalescence (, ll'JO intranetal l-polymer (Also in the graph l-cross agent ill tj is extremely important and the f↑11-100 of the above component (A+')-(^,')
It is used in an amount of 11 to 5 parts by weight, preferably 15 to 2 parts by weight.If the lid is less than 1 part by weight, the effectiveness of graft bonding will be low and the interlayer Q-bond will be insufficient.

Moreover, when μ exceeds one part of pentacarbonate, 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 j@1 coalescence (A') t *-) is a layer with i-grafting activity, and its TgtJ is appropriately set according to the physical properties required of the ms polymer. Further, the crosslinking density t, 1, is generally the same as, or even higher than, that of the crosslinked elastic polymer (B'), which is advantageous in terms of quality. Note that the innermost layer polymer (A'
) and a crosslinked elastic polymer (B is the same group (21)), but it is important to have a two-layered elastic body structure by two-stage polymerization rather than one-time injection. Regarding the setting of the catalyst amount, crosslinking density, etc., it is advantageous that the polymer (A) is higher.

Considering initial polymerization, the presence of the innermost Si polymer (A') is extremely important in order to obtain a stable multilayer structure polymer, and in general, a large amount of catalyst is added to each polymer layer.

The use of a graft cross-agent is essential for effectively synthesizing a two-layer elastic structure chemically bonded to the cross-linked elastic monomer (B') formed in the second stage. Without this graft bond, the two-layer elastomer structure would easily undergo phase destruction during melt molding, reducing rubber efficiency, and would 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 [11] is 5 to 40% by weight, preferably 5 to 20% by weight, and is certified to be less than the content of the crosslinked elastic polymer (B'). It is.

(28) Next, the crosslinked elastic polymer (t+') is a multilayer structure polymer [1]
It is the main component that provides excellent flexibility and has a Fi of 50 to 1, preferably 35 to 6 in the multilayer structure polymer [l].
Occupies a ratio of 01-excellent. If the proportion of the crosslinked elastic polymer (B') is less than 3011 Jil, sufficient flexibility will not be achieved, whereas if it exceeds 80 Jil, workability etc. will be significantly lowered, which is not desirable.

Each component constituting the crosslinked elastic i-superstructure (H') is as follows:
Above 1. *Multilayer structure 1 combination [ll crosslinked elastic polymer (B
) t-The same components as those constituting each component are used. This is the same for the outermost layer polymer ((:l') # and intermediate layer (D) in the iJ multi-structure polymer [111], and the same applies to the above-mentioned multilayer structure polymer [ID outermost layer polymer ( (]) and the intermediate layer CD).

Also, in the crosslinked elastic polymer (B'), its individual '
It goes without saying that the rg is low, and particularly favorable physical properties can be obtained at temperatures below -30°C. In addition, a multi-JIll structure polymer [also in ID, the two-layer crosslinked elastic body has a gel content of 85 or more and a swelling degree of 3 to 15, determined by the method described above (2ν). It is necessary to be present.

The content of the outermost layer polymer (C') in the multilayer structure polymer [■] is 10% by weight or more and less than 50% by weight.

In addition, even in the outermost layer polymer, its individual Tg is 60°C or higher in order to obtain excellent solvent resistance and water whitening property.
Preferably, the temperature needs to be 80°C or higher. If the Tg of the polymer (0 alone) is less than 60°C, satisfactory physical properties cannot be obtained.

The content of each intermediate layer (D) in the multilayer structure polymer [■] 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;
If the weight exceeds 5, the final polymer will be unbalanced.

If the content of the entire intermediate layer exceeds 40% by weight, the overall balance will be lost, which is not preferable.

Preferably, the gel content of the final polymer of the multilayer structure polymer [11] is in the range of 60 to 95 weight-ms (30).1. stomach. If the gel content is less than 60% by weight, the solvent resistance will decrease, and if it exceeds 95% by weight, the forming force will decrease even when blended with the multilayer structure [1]. (I don't like it.

The above multilayer structure 3&polymer [13 and (113if) can be obtained by sequential multistage polymerization f1 method by emulsion polymerization method, but especially this V (without limitation, for example, Jl layer polymerization +2 after emulsion polymerization) * It can also be obtained by the emulsified M-soak method, which is converted into suspension polymerization at the same time.In addition, emulsifiers, catalysts, and coagulants are particularly regulated4. (1)
No.

Naota 1m structure 11! -8 bodies [1] and [11] Emulsion particles of the final polymer +! eJ There is no particular limit, but 80
The most balanced structure can be obtained in the range of about 0 to 2000 μm. The latex of these multilayered polymers is subjected to salting-out treatment by adding additives such as antioxidants and lubricants as necessary.

The multilayer structure polymers 11 and (il) have similar polymer structures, and it is preferable from the viewpoint of transparency etc. that only the ratio of each layer is different. However, depending on the purpose, (61) can be completely different alkyl ( It goes without saying that it is also possible to use those obtained from meta)acrylates.

The blending ratio of multilayer structure polymer [1'll and multilayer structure polymer [01] is 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 to achieve the purpose. It can be set as appropriate.

For example, when particularly fluidity is required, such as when molding into a film by the T-gui method, a multilayer structure polymer [the blending ratio of ID is 50 parts by weight or less, preferably 10 to 10 parts by weight] is used.
It is desirable to keep the content within the range of 40 parts by weight. On the other hand, for applications that require extremely flexibility, it is of course desirable to use the multilayer polymer [■] in an amount of 50 parts by weight or more, preferably in the range of 50 to 90 parts by weight. A multilayer structure polymer [A resin composition containing 50 parts by weight or more of ID is a multilayer structure polymer [although the fluidity is certainly lower than a resin composition containing 50 parts by weight or less of ID, it is possible to form a thin film with a T-die ( 52) I do not experience any difficulty in molding, except when molding.

Multilayer structure polymer [! ] and the multilayer polymer [1] can be blended by blending the powders of each powder using a Henschel mixer in a conventional manner, or by mixing the respective latexes and then performing a salting-out treatment. It can also be blended by this method.

Also, when blending the multilayer structure 1 combination [1] and the multilayer structure polymer [11], ultraviolet #! General additives such as absorbers, tII inhibitors, pigments, and shavings can also be added, especially when adding purple stain 1 and line absorbers ↓ shi even more weather resistant +'4
．． ff-J [3°] Also, the 41-structure ItI combinations of the present invention may be blended in the above proportions.1. The above-mentioned polymer (
At least one polymer selected from the group 1) or (11), or S from each group of polymers (1) and (11)
The mixture of at least one type of electrolyte obtained is 99-1
] [It is possible to mix (65) separately.

Multilayer structure polymer [1] and [1] used in the present invention
13U The innermost layer polymer (A
) or presence of (A'))-, a cross-linked elastic W combination (B) or (B') containing an alkyl acrylate as a main component is polymerized, and the outermost layer contains alkyl methacrylate as a main component with a low Tg and a 0 degree Celsius. QH layer polymer (C) or (C')
The amount of alkyl acrylate between the polymer (B) or (B') layer and the polymer (0) or (C') layer is The polymer (0) or (C'
) layers are effectively graft-bonded,
It also has a multilayer polymer structure with a specific gel content, so when blended with other compatible thermoplastic resins with different refractive indexes, it has excellent transparency and no stress whitening. 14, especially methyl methacrylate-1 (64).
・Transparency when combined with hanging fat.

It can be said that the resin composition has excellent 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 special structure of the multilayer polymers [I] and [11], and cannot be predicted from conventional methods of introducing rubber components.

＼ Vinyl chloride tree Jll again! f, polystyrene, muS resin, polycarbonate 1. When blended with resin, the blend composition of multilayer structure lI & body [-1] and [113 t has a kind of weatherability, -1 impact modification 1, which acts as a weathering agent and brings about a significant improvement in weather resistance and weather resistance1.Furthermore, the blend composition with polyvinyl heptadide has weather resistance, IN 1111? 1. It has excellent stress whitening resistance, chemical resistance, toughness, and moldability.
In particular, a resin composition consisting of 1 to 50 (55) parts by weight of polyvinylidene fluoride and 50 to 99 parts by weight of a blend composition of multilayer structure polymers CI] and [ll] is excellent as a material for film molding, and is transparent. Strong weather resistance,
Provides a film with excellent stress whitening resistance, chemical resistance, etc. Such a film can easily impart weather resistance and a design effect by laminating it on the surface of an ordinary molded article, and has extremely high commercial value.

The present invention will be specifically explained below using Examples.

In addition, both "1 part" and "1 part" in the examples are "parts by weight."
and ] heavy weight. In addition, the abbreviations used in the examples are as follows.

MMA: Methyl methacrylate MA: Methyl acrylate BuA: Butyl acrylate 2FiHA: 2-ethylhexyl acrylate Bt:
Styrene BD: 1. ! l-butylene dimethacrylate AMA:
Allyl methacrylate OHP: Cumene hydroperoxide (36) 8) 1'S: Sodium aluminum aldehyde sulfoxylate The Tg of each electrolyte layer used in the examples is, for example, the Tg listed in the Polymer Handbook. From the value of ft
-4M) -CToru.

1 part, esterunda salt of sulfur A succinic acid, 2 parts, SFB
After charging α05 parts and stirring under a stream of air, 1.6 parts of MMA,
BuA 8 parts, Bl) α4s, AMA (11 parts and O
A mixture consisting of 4 parts of HP CL O was charged.

The temperature was raised to 70° C. for 30 minutes) to complete the IN process of the innermost layer polymer (A). Next, 1.5 parts of MMA,
22-5 parts of NuA, 1 part of January], 25 parts of AMA a, and a mixture of these were mixed with OHP of α05.1. The mixture was added over 5 minutes, (37
) The mixture was held for an additional 60 minutes to polymerize a two-layer crosslinked elastic body consisting of two layers of polymers (A) and (B). Swelling degree Fi1α of the thus obtained two-layer crosslinked elastic body in MPK
0, the gel content was 90%.

Next, 5 parts of MMA, which corresponds to the intermediate layer (D), and 5 parts of BuA
1 part of AMA Q was added over a period of 10 minutes to polymerize, and finally 52.25 parts of MMl,
A mixture of 2.75 parts of BuA was similarly polymerized using OHP corresponding to 11% of the monomer amount used in each layer.

Similarly, multilayer structure polymers CI-+2+] to [I-(5
1], comparative polymers (1), (2), and (3) were polymerized.

In all cases, the final particle diameter was 1000 to 1500A.

These polymer latexes were salted out according to a conventional method, washed, dehydrated, and dried to obtain dry powder.

Their compositions and physical properties are shown in Table 1.

(2) Production of multilayer structure polymer [■] (68) Multilayer structure polymer [I
], a 41-shaft structure vehicle combination [1] having the polymer structure shown in Table 2
(-(1)]~[■-(51]1&, hiJl[,*
Combined +41 t 113 combined.

The S# particle size of Kowara Municipal Corporation is all 1000-1
500A17) Range 11 (', ,i, Tsuta.

These polymer latexes were also salted out according to a conventional method, washed, dehydrated*, and dried to obtain dry powder.

Their compositions and physical properties are shown in Table 1.

(39) (3) Preparation and evaluation of resin compositions Multilayer structure polymer CI-+11] and [It-+11]
] were blended in the proportions shown in Table 3, 2 parts of an ultraviolet absorber (trade name: Tinuvin-P, manufactured by Ciba Geigy) were added, mixed well, and pelletized using an extruder.

The obtained pellets were dried at 70° C. for a day and night, and then molding processability was tested using an injection molding machine. The results are also shown in Table 6. The criteria for determining moldability are as follows.

Evaluation criteria for moldability S: 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.

Furthermore, using the same pellet, the thickness was 250 mm using the T-die method.
A sheet of μ was molded. For samples that could be molded into good sheets, the transparency (total light transmittance and chain side) was evaluated based on JIS K 6714, and the tensile modulus was measured as a measure of flexibility. For samples (42) and (41) for which a good sheet could not be obtained, the tensile modulus was not measured, but 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 knitting test was performed using a Sunshine Weather-Ometer, and the retention rate of elongation at break was determined from the tensile elongation measurements before and after the test. And so. These measurement results are also shown in Table 6. In addition, multilayer structure 1 combination [1-
(1)]□~CI 151L [ll-111]~[
II −+51 ] and comparative polymer ill~(4) were blended in the proportions shown in Table 4, and the same evaluation was performed.

The evaluation results are shown in Table 4. All of the products of this invention have transparency,
It has excellent weather resistance, as well as appropriate flexibility and workability. Note that the ratios (11 to (4)) in Table 4 indicate comparative polymers 0) to (4).

(43) Example 2 Multilayer structure polymer CI −(+l]7 synthesized in Example 1
0 parts and multilayer structure polymer C11-fxl ] 3o parts (present invention example (21)) 50 parts of MMA
/MA copolymer (MMA/MA -99/1 ratio.

ηSP/. -[1,60 (measured with α10 f/dt kneading solution)) So part was blended using a Hennel mixer, and then pelletized using an extruder.

The obtained pellets were dried at 80° C. for a day and night, and a sheet having a thickness of α5m was formed using a T-die.

This blended polymer had good sheet formability, and a sheet with excellent transparency, gloss, etc. was obtained. Furthermore, a two-part thick injection molded plate without injection molding was obtained using the same pellets. The total light transmittance and Dynstadt impact strength of the obtained molded plate were measured. The total light transmittance was 95 inches, and the Dynstadt impact strength was 65 o.cnv'ca;', showing extremely good values.

Further, the above-mentioned molded plate was subjected to an accelerated exposure test (46) for 30 LIO hours using a Zanshine Weather-Ometer, and the gloss retention rate was measured. Gloss retention rate is 9
4, which is extremely high, indicating that the product of the present invention is also excellent in weather resistance.

Example 6 Multilayer structure 1 composite CI- (In2O part, multilayer structure polymer [II-f+lso part) synthesized in Example 1 and 10 parts of polyvinylidene fluoride (trade name: Kynar 500°, manufactured by Pennwalt Co., Ltd.) were mixed together. After blending with Elmikya,
It was made into a shilet using a screw type extruder. The obtained pellets were formed into a film with a thickness of 80 μm by an inflation method.

Tensile strength and elongation (J-Ko SZ 17
0-2), haze value (ASTM-D 1003-61
) was measured. Tensile modulus 8X10mKg/
1m", breaking strength 340 K17cm2. breaking elongation 20
Both showed very good values of 0 Excel and haze value of 4.8.

The obtained film was bonded to a galvanized 0.5 tea cold-rolled steel plate using an adhesive and this bonding (47) was carried out on the sample. 1. Conducted at a height of 450[alpha] and a temperature of 20[deg.] C.), no cracks showing whitening were observed in the porcelain part.

Furthermore, an accelerated exposure test of 3111111 hours was carried out using a weatherometer to measure the tensile strength and elongation after exposure. The retention rate of tensile elongation of the sample (1111, the elongation of the unexposed product is 100 cm, ',: L, etc.; it is a measure of the tendency and susceptibility) was 90%. , The product of the present invention is suitable for Fi (having excellent weather resistance) 1, t, 7'?,.

1st Permit Applicant - Ai 1/ -11-17 Co., Ltd. Agent 41” Rito Toshio Aozawa (48)

Claims (1)

[Scope of Claims] 1 to 99 parts by weight of at least one type of multilayer structure polymer [ID] and at least one of the multilayer structure polymers
A thermoplastic resin composition consisting of parts by weight. 2 1 to 99 parts by weight of a resin blend consisting of 1 to 99 parts by weight of at least one kind of multilayer structure polymer CD and 99 to 1 parts by weight of at least one kind of multilayer structure polymer [■], and the following (1)
or by blending 99 to 1 part by weight of at least one polymer selected from the group (11) or a mixture of at least one polymer selected from each of the groups ti (i) and c i ). A thermoplastic resin composition. Polymer (1): A homopolymer of a monomer having the following general formula (a), (1)) or (C) or a copolymer consisting of two or more of these monomers. OH2-OX Y * e @ @ @
(a) (1) However, in the formula, X and Y are H, C1, F, Br, OH3
゜coon, 0OOcH3,ON,
000('H,,0@Il,. Alkoxy group, either 0OOH3, 80sH. OF,=OFZ ■ooo(b) However, 2 in the formula is either H, ?, 01.OFB. 0Hx-0-000R·Φ...(C)Hs However, R in the formula is a fluoroalkyl group. Polymer (ii): Polycarbonate, thermoplastic polyester. Polyamide.