JPS5951931A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved impact resistance, prepared by mixing a vinyl chloride resin with a copolymer obtained by graft-polymerizing a specified vinyl monomer in the presence of a rubber polymer prepared by polymerizing an aqueous dispersion containing an alkyl acrylate and a catalyst. CONSTITUTION:A composition comprising ( I ) 3-70pts.wt. copolymer obtained by graft-copolymerizing 80-20pts.wt. at least one member selected from the group consisting of a lower-alkyl methacrylate, an aromatic vinyl and an unsaturated nitrile or a mixture thereof with other monomers copolymerizable therewith in the presence of 20-80pts.wt. rubber polymer obtained by polymerizing an aqueous dispersion containing 80-100wt% 2-8C alkyl acrylate, 0-20wt% other monomers copolymerizable therewith, a crosslinking monomer, a monomer- soluble catalyst and an emulsifier without adding any fresh catalyst and (II) 97-30pts.wt. vinyl chloride resin or a copolymer comprising at least 70wt% vinyl chloride and other copolymerizable ethylenic monomers copolymerizable therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition having excellent weather resistance, impact resistance, mechanical properties and processability. Specifically, the present invention relates to a vinyl chloride composition comprising vinyl chloride or a vinyl chloride copolymer and an acrylic modifier produced by a novel polymerization method.

Although vinyl chloride or vinyl chloride copolymers (hereinafter referred to as vinyl chloride resins) have good mechanical and chemical properties, they have the drawback of poor impact resistance. In order to improve this impact resistance, modifications such as those based on conjugated diene rubbers grafted with acrylonitrile and aromatic vinyl (ABC type) and those grafted with alkyl nysterte aromatic vinyl methacrylate (MBS type) are used. However, such modifiers have poor 1lliJ properties because they use a comb with an upwardly tilted 2-ton bond.
Disadvantage 4: If left outdoors, it deteriorates rapidly.
・Have it.

As a method to overcome this drawback, an acrylic acid alkyl ester polymer that does not have double viscosity at +6゛C1 obtained by emulsion polymerization is used. A method using an acrylic modifier obtained by emulsion graft polymerization of a monomer of a compound or a monomer K M it has been proposed. (For example, special train 11/j 46-22114
(No. 2, No. 46-88: 345) However, this method does not require the use of acrylic acid alkyl esters 11
In order to obtain a type 11 elastomer, one such polymer is grafted by conventional emulsion polymerization. '(
Perhaps because it is not possible to obtain a copolymer having a graft structure as in the case of ABS resin, there is a disadvantage that the effect of improving the impact resistance of vinyl chloride resin is insufficient.

Regarding the improvement of such defects, special report 11/l 47-429
No. 9 discloses a method of suppressing the photogenesis of new particles in a kraft chassis by limiting the amount of emulsifier used during kraft polymerization; A method has been proposed that uses a special expensive crosslinking monomer to enhance the crosslinking effect and make it easier to form a graft structure. Therefore, the particles of comb polymer are 0.0
Since the particles are small (5 to 0.3μ), the impact resistance is not sufficiently improved, and even if larger particles are obtained by seed polymerization, the emulsion graph is low. This may be because the impact resistance is not sufficiently improved, and in addition, when the amount of emulsifier is limited, the stability of polymerization is inhibited and there are disadvantages such as increased lees formation.

As a result of extensive research into methods to improve these drawbacks, the present inventors homogenized a water-dispersed thread containing an acrylic acid alkyl ester, a crosslinking monomer, and an emulsifier using a catalyst soluble in the monomer. By post-heating polymerization and subsequent polymerization of a vinyl-based polymer that increases compatibility with vinyl chloride-based resins such as alkyl methacrylate esters, without substantially adding any new catalyst, conventional emulsion polymerization is possible. A rubber polymer with a large particle size that is difficult to obtain can be easily obtained, and the resin component that is compatible with the vinyl chloride resin sufficiently binds the rubber. It was discovered that the impact resistance strength was improved to W4,
The present invention has been achieved.

Also, in the case of (i), the present invention provides that the [I] alkyl group has 2 to 2 carbon atoms.
Acrylic acid allyl, ester 80-10
r) Weighted %, other varnish copolymerizable with the varnish ()
Gol-polymer (A) obtained by homogenizing an aqueous dispersion containing ~20% by weight of a crosslinkable monomer and a catalyst and an emulsifier soluble in the monomer, followed by polymerization. In the presence of a stirring section.

Rubber polymer (
The catalyst included in 2) at least one monomer selected from the group consisting of lower methacrylic acid alkyl esters, aromatic vinyls and unsaturated nitriles, or said monomer and other copolymerizable monomers therewith. Graph 1 obtained by graft copolymerizing 80 to 20 parts by weight of a small amount mixture (B) consisting of 0 to 30 parts by weight of a monomer, and 3 to 70 parts by weight of a copolymer, and [IrF vinyl chloride vinyl resin] This invention provides a vinyl chloride resin composition comprising at least 70% by weight of vinyl chloride and 97 to 30 parts by weight of a copolymerized resin with another ethylene monomer capable of copolymerizing 1 iJ. .

[1] The graft copolymer, which is one of the components of the composition of the present invention, is produced according to the recipe described below.

The acrylic acid alkyl ester used in the production of the rubber polymer of the present invention is an intermediate in which the alkyl group has 2 to 8 carbon atoms, examples of which include ethyl acrylate, propyl acrylate, acrylic acid Examples include n-butyl acrylate, pendel acrylate, hexyl acrylate, n-ocdyl acrylate, 2-ethyl l\xyl acrylate, and the like. These monomers can be copolymerized up to 20i31% with C1 functional monovinylidene compounds, and as an example of such copolymerizable monovinylitine monomers, styrene , vinyltoluene, α-
H6 group vinyl monomers such as nodyl styrene; unsaturated nitriles such as acrylonitrile and methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butylhinyl ether and octyl vinyl ether; methyl methacrylate and ethyl methacrylate. Examples include methacrylic acid alkyl esters such as. It is preferable to select the type of monomer and the amount of copolymerization so that the glass transition temperature of the rubbery heavy a-form is -10°C or lower. In carrying out the present invention, it is necessary that the rubber copolymer (A) be a copolymer of an acrylic acid alkyl ester and a crosslinkable TP polymer in order to improve the impact resistance of the final composition. . If the crosslinkable monomer is not copolymerized, it is not preferable because a sufficient effect of improving impact resistance cannot be obtained and the processability of the chlorinated vinyl resin composition is reduced.

The amount of crosslinking monomer used is 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total monomers for the comb polymer, and if it is less than 0.1% by weight, If a sufficient crosslinking effect can be obtained, if the amount exceeds 10% by weight, the degree of crosslinking becomes excessive, which is not preferable because impact resistance tends to decrease. Examples of crosslinkable monomers include di- and tri-methacrylic and acrylic esters of polyhydric alcohols (
ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate-1-1l, 8-butylene glycol dimethacrylate, etc.), divinyl ethers of polyhydric alcohols (ethylene glycol divinyl ether, etc.), divinylbenzene, allyl compounds ( (diallyl phthalate, diallyl maleate, triallyl cyanurate, allyl methacrylate, allyl acrylate, etc.), and these crosslinkable monomers may be used alone or in combination of two or more.

The catalyst used in the present invention must be soluble in the above monomer mixture, and examples of such catalysts include organic peroxides such as benzoyl peroxide, lauroyl peroxide, 1. -Butylperoxybenzoate, -butylperoxypivale-1, etc. and aso compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, etc. can be used alone or in combination.

These oil-soluble catalysts are usually used in a proportion of 0.2 to
Although 2% by weight is used, the optimum amount can be easily determined by preliminary experiments depending on the type of catalyst used and polymerization conditions.

It is also desirable to add all or most of the amount of catalyst used to polymerize all the monomers to the system before homogenization, but if necessary, it is also possible to add more before graft polymerization. be.

Further, the catalyst may be added all at once during the polymerization process of the acrylic acid alkyl ester [7, and may be added in portions.

Anionic emulsifiers, nonionic emulsifiers, and cationic emulsifiers can be used as emulsifiers, but in order to obtain a fine emulsified liquid in the homogenization step and to stably proceed with polymerization, Lauryl sulfate i +-! Higher alcohol sulfate esters such as Jum, dodecylbenzene sulfonic acid! - It is desirable to use anionic emulsifiers such as alkylaryl sulfonic acid salts such as sodium chloride, and aliphatic salts such as sodium olefinate. Further, higher alcohols, nonionic emulsifiers, etc. can be used in combination with the anionic emulsifier. The amount of emulsifier used is also related to the dispersed droplets of the monomer mixture obtained by the homogenization process, and is determined together with the operating conditions for homogenization, but in general, the amount of emulsifier used is It is used in an amount of 0.2 to 5% by weight. Further, a part of the emulsifier can be appropriately added after homogenization or during the polymerization reaction.

In producing the comb polymer of the present invention, the aqueous dispersion containing the above-mentioned acrylic acid alkyl ester, 1'i4 for crosslinking, catalyst and emulsifier is subjected to strong shearing force prior to polymerization. Homogenized by applying fine 14 + 1 suspension 4
・To be done. The particle size in the rubber polymer depends on the average dispersed particle size of the monomer in the homogeneous treatment, and the particle size of this rubber polymer is the same as that of tony chloride when the graft copolymer is mixed with the vinyl chloride resin. In general, it is preferable that = f J and the average particle size of the polymer be about 2 tt or less, more preferably 0.2-1 p, since this will affect the properties of the ladle composition. Adjustment of the average dispersed particle size can be easily achieved by adjusting the amount of emulsifier used and operating conditions specified in 7 during homogenization treatment.
(It will be done.

For this purpose, co[1 Idmil, homogenized →)°
-, a known homogenizing device such as a flow jet mixer, a homomixer, etc. can be used.

F-J During the homogenizing treatment (7), even if the entire amount of the acrylic acid alkyl ester and crosslinking monomer is homogenized, some of the acrylic acid alkyl ester and crosslinking monomer are homogenized to facilitate the removal of the polymerization heat. The remainder can also be added continuously or part-time during the polymerization process.

The homogenized acrylic acid alkyl ester and crosslinkable monomer are then subjected to polymerization.

The polymerization temperature during polymerization of acrylic acid alkyl ester can be determined as appropriate depending on the catalyst used, but is usually 40°C.
~80°C is adopted. It is desirable that the stirring be carried out gently enough to prevent agglomeration in the fractionating section.

After polymerizing the acrylic acid alkyl ester, in order to increase the compatibility with the vinyl chloride resin, the catalyst is substantially renewed in the presence of 20 to 80 parts by weight of the obtained rubber polymer. At least one monomer or stiff monomer selected from lower methacrylic acid alkyl esters, aromatic vinyls, and unsaturated nitriles and a stiff monomer are combined with the catalyst contained in the comb polymer (5) without addition. Polymerization (7 obtained monomer mixture (B) consisting of 0-30% by weight of other monomers 80-2
Graft copolymerize 0 parts by weight.

The composition of the resulting graft copolymer has a great influence on the properties of the resulting vinyl chloride thread resin composition. The weight of the acrylic acid alkyl ester copolymer is 20 parts or more.
The copolymer does not have sufficient ability to improve the impact strength of the resulting vinyl chloride thread resin composition, and it is recommended that the copolymer has less components compatible with vinyl chloride resins than -80,000 parts. This is not preferable because the impact strength of the polyhinyl chloride resin composition becomes insufficient and the processability deteriorates. ) ~ 80 @ π and unsaturated nitrile-containing monomers Q) 0 to 20% by weight of monomers capable of combining 1 to 1, or (2) 40 to 80% by weight of aromatic vinyl compounds; Fof foam hit Doni 1-Lil 1 () ~ 50i Kuma'! g and other copolymerizable compounds containing ivy acrylic acid alkyl esters - H form 0 in 〇 = - 20 i1j storage%, or (3) methacrylic acid alkyl esters 20 to 70 heavy electricity. Q, aromatic vinylated substance 10~60%, unsaturated nitrile 2
0 to 50 @l]% and other copolymerizable monomers 0
~20% by weight of the three monomer components are preferably used. Methacrylic acid alkyl ester is a compound having an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, and n-butyl methacrylate. , can be used alone or in combination. Examples of the aromatic vinyl compound include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and the like. Further, examples of the vesicular nitrile include acrylonitrile and methacrylonitrile.

Up to 20% by weight of each of the above monomers can be substituted with other monomers copolymerizable with the monomers, such as acrylic ester, acrylamide, methacrylic acid, and carbon atoms having 5 carbon atoms. Examples include methacrylic acid alkyl esters, alkyl vinyl ethers, and alkyl vinyl esters having the above alkyl groups. These monomers may be polymerized together with a crosslinkable monomer to crosslink all of them, or C may be partially crosslinked. Graft copolymerization is generally carried out at 50-90'C. The monomer can be applied to the entire line at once, or by adding portions of it continuously or incrementally.

Historically, ffi rlc compounds may be used by mixing the components used in the operation, but it is also possible to polymerize in two or more stages while keeping the composition within the above range of components that can satisfy compatibility. can.

After grafting, the aqueous dispersion of the graft copolymer is recovered by spout drying or by salting out, coagulating, washing and drying. At this time, it can also be photocoagulated with an aqueous dispersion of vinyl chloride-based fat. Furthermore, anti-aging agents, heat stabilizers, processability improvers, etc. can be added during coagulation.

rnl which is another component of the vinyl chloride composition of the present invention
JA Hinibini fertilizer or at least 70% vinyl chloride
A copolymer of Kisei % or more and other ethyl monomers that can be copolymerized with this is made by a known method at 1% and is the first available vinyl chloride resin composition of Komei Ichiki. In [
The blending ratio of [I] graft copolymer and [m] hinivinyl chloride resin is generally 8 to 70 parts by weight: 97 to 30 parts by weight, preferably 5 to 50 parts by weight - 95 to 50 parts by weight.

[11 If the amount of the graft copolymer blended is less than 3 parts by weight, the effect of improving impact resistance will be poor, while if it exceeds 70 parts by weight, the effect of adding the vinyl chloride resin will be lost, which is not preferable.

The mixture of the graft copolymer and the vinyl chloride resin can be processed using a roll, a Banbury mixer 1 extruder, an injection molding machine, or the like.

In addition to heat stabilizers, this composition also contains light stabilizers, solvents, fillers,
It is also possible to add antistatic agents, processing aids, or, if necessary, small amounts of solubilizers. The composition of the present invention may also contain other polymers that can be mixed with the vinyl chloride resin, such as ethylene-vinyl acetate copolymers, ethylene-acrylic ester copolymers, and ethylene-methacrylic ester copolymers. and graft copolymers of these copolymers and vinyl chloride, styrene-acrylonitrile copolymers, styrene-methacrylic acid ester copolymers, AB
It is also possible to blend G-vinyl chloride resin with S-based resin, 1MB5-based resin, acrylonitrile-butadiene-based resin, chlorinated polyethylene, etc. This will be described in detail with examples below. Note that the deviations (parts and percentages) in the examples are also based on the claw kite standard.

Example 1 (Preparation of graft copolymer) A coarse dispersion containing the following materials is prepared in a stirred vessel.

z1-Butyl acrylate 60 parts Dodecylbenzene sulfonic acid sorter 1.0 part Triethylene glycol dimethacool (i, 2 parts) Lauroyl peroxide 0.6 part Distilled water
200 parts of the above coarse dispersion was homogenized by passing it through a Manton-Gallin type two-stage high-pressure pump homogenizer (first stage pressure 150 Kg+J, second stage pressure 30-1), then a stirrer, thermometer, and reflux condenser were used. The mixture was charged into a prepared polymerization reaction tank. After the polymerization reaction III was heated to 70°C and reacted for 2 hours, a small amount of the dispersion was collected, and the polymerization rate was determined from the solid content concentration, which was 98%, and the average particle size calculated from the turbidity was 0. It was 6μ. Further, the sampled liquid was salted out and coagulated, and after drying, the toluene insoluble content was determined to be 95%.

Next, while keeping the polymerization reaction tank at 70°C, 40 parts of methyl methacrylate was added dropwise for 2 hours (after dropping, the reaction was carried out at 80°C for 2 hours. The polymerization rate was 9.8%. Ta.

The obtained aqueous dispersion was salted out and coagulated with calcium chloride.
y t = Post-dehydration, washing and drying.

(Preparation of vinyl chloride resin composition) 18 parts of the acrylic modifier obtained above was mixed with an average polymerization degree of 1.
000 vinyl chloride resin and 2 parts of tribasic lead sulfate.
1 part, stearate] 1 part of lead stearate, 0 parts of calcium stearate
．． A sample was prepared by mixing 5 parts of the sample with a heat roll at 170°C for 5 minutes and press-molding at 185°C. Notched Izot impact strength (l) at 20°C according to the usual method
/8 inch thickness) and tensile strength were measured, and the results shown in Table 3 were obtained.

Table 8 shows 5 of the obtained vinyl chloride resin composition.
Here are the results of the 00 hour Weatherometer exposure test.

It can be seen that the samples obtained according to the present invention have high impact strength, good melt flowability, and are excellent in weather resistance.

\ \ \ \ \ \ \ \ \ Examples 2 to 5 In the same manner as in Example 1, except that 40 parts of methyl methacrylate in the graft mass was replaced with the JP mass mixture shown in 1fi. The kraft copolymer thus obtained was made into a vinyl chloride thread resin composition in the same manner as in Example 1. The results are shown in Section 3.
He's talented on the outside.

No. 1 Clothing Examples 6 to 8 Except for using 1.2 parts of the crosslinking monomer shown in Table 2 instead of 1.2 parts of triethylene glycol dimethacrylate, which is a crosslinking agent, in Example 1. A kraft copolymer was produced in the same manner.

Furthermore, after polymerizing 11-butyl acrylate, a portion of the sample was sampled and examined, and the average particle diameter and toluene insoluble content were as shown in Table 2. A vinyl chloride resin composition was prepared in the same manner as in Example 1. The results are shown in the third column.

Table 2 Comparative Example 1 An aqueous dispersion containing the following substances was maintained at 60°C with stirring.

Distilled water 200 parts Sodium dodecylbenzene sulfonate 0.08
Part ethylenediaminotetraacetic acid disodium 0.01
Ferrous sulfate heptahydrate 0.005
0.5 parts sodium phosphate decahydrate, 60 parts n-butyl acrylate, 1 part triallyl cyanurate
．． 2 parts of cumene hydroperoxide, 0.1 part of 5% of the monomer mixture. After 10 minutes, 0.3 parts of dodecylbenzene sulfonic acid sorter was added, and 95% of the remaining monomer mixture was continuously added dropwise over 4 hours. After dropping, mold mixing was carried out for 1 hour, and after that, a small amount of dispersion was collected, and the polymerization rate was determined to be 98%, and the average diameter (calculated from turbidity) was 0.1
5 It was. Moreover, the toluene insoluble content was 94%.

Next, after adding 0.2 parts of Rongarinoto to the above dispersion,
At 60°C, a mixture of 40 parts of methyl methacrylate and 0.08 parts of cumene hydroperoxide was added in 2 hours, and then maintained for 1 hour to complete the polymerization. The obtained aqueous dispersion was salted out and dried in the same manner as in Example 1' to obtain a powdered resin.

The graft copolymer thus obtained was treated in the same manner as in Example 1 to form a -C chlorinated Hibini thread resin composition. Results @
It is shown in Table 8.

Comparative Example 2 10 parts (as rubber solid content) of an acrylic rubber emulsion (average particle size 0.15/') obtained in the same manner as in Comparative Example 1 and the following components were stirred and maintained at 60°C.

Distilled water 200 parts (total amount) Dotecylbenzenesulfonic acid sorter 0450 Ngarinoto 045 Ethylenecyaminetetraacetic acid disodium 0015 Ferrous sulfate heptahydrate 0005 Sodium phosphate dodecahydrate 0.5 Next 11-butyl acrylate 100 copies,
A monomer mixture of 1 to 2 parts of realyl cyanurate and 0.15 parts of cumene hydroperoxide was continuously added over 4 hours to obtain 3 parts of an aqueous dispersion of Gol and Ig combined with an average particle size of 039 μm. The toluene-insoluble content of this product was 93%. Next, 40 parts of methyl methacrylate was subjected to emulsion graft polymerization in the same manner as in Comparative Example 1 in the presence of 60 parts (as rubber solid content) of the obtained rubber emulsion, and treated in the same manner. The graft base material thus obtained was treated in the same manner as in Example 1 to form a B vinyl resin composition. The results are shown in Table 8.

Comparative Example 3 Example 1 except that a commercially available MBS-based modifier Kaneace l'3-12 was used as a kraft copolymer.
A vinyl chloride resin composition was prepared in the same manner as f:, and the results are shown in Table 3.

Example 9 11 to 30 parts of butyl acrylic acid in which 0.6 part of lau τ co-yl peroxide was dissolved, 20 parts of dotecylbenzenesulfonic acid sorter, 1. After preliminarily stirring 6 parts of s-butylene glycol dimethacrylate hO and 200 parts of distilled water in a reaction tank, polymerization was carried out through a homomixer (pipeline homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.) connected to the polymerization reaction tank. Recirculated to tank. 10 The entire amount of the homogenized dispersion was returned to the reaction tank and heated to 70"C1. After 1.5 hours,
A monomer mixture of 30 parts of 11-butyl acrylate, l,3 butylene glycol dimethacrylate and 1-0.6 parts is added and after a further 1.5 hours, 40 parts of methyl methacrylate are added over 2 hours. The polymerization reaction solution was sampled before the continuous dropwise addition of methyl methacrylate, and the fA ratio of II-phthyl acrylate was determined.9
It's 5%. The average particle size per cubic meter was 0.9μ. ! The aqueous dispersion after polymerization was treated in the same manner as in Example 1 to prepare a vinyl chloride resin composition [7]. Izo of this,
1-Impact strength was 84 Kfrm/cd and tensile strength was 485 Ky/di.

From -L

Claims (1)

[Scope of Claims] [I] Acrylic acid alkyl ester whose alkyl group has 2 to 8 carbon atoms 80 to 100% by weight, and 0 to 20% by weight of other monomers copolymerizable with the ester 9fr
, a water molecule containing a crosslinking monomer and a catalyst and an emulsifier soluble in the monomer19. The system is subjected to homogenization treatment t7, and then the existence of 20 to 80 heavy sensitive parts F in the rubber polymer obtained by polymerization is reduced to ``lower methacrylic by the catalyst contained in the rubber polymer without substantially adding a new catalyst. At least one monomer selected from the group consisting of acid alkyl esters, aromatic vinyls, and unsaturated nitriles, or 0 to 30% of the monomer and other monomers copolymerizable therewith.
Graft copolymer 3 to 1 obtained by graft copolymerizing 80 to 20 parts by weight of a homopolymer mixture (J3) consisting of
70 heavy tails, and [1[] Vinyl chloride resin or a copolymer resin of at least 70% by weight of vinyl chloride and other copolymerizable ethylene monomers from 97 to 30 parts by weight. A vinyl chloride resin composition.