JPS61258850A - Vinyl chloride based resin composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating a specific amount of a polymer, having a three-layer structure, and prepared by polymerizing an aromatic vinyl compound with an acrylic acid ester and methacrylic acid ester one after another, having improved mold release characteristics in molding thereof and capable of giving molded articles having improved gloss and transparency. CONSTITUTION:A vinyl chloride based resin composition obtained by incorporating (A) 100pts.wt. vinyl chloride (co)polymer consisting of >=80wt% vinyl chloride units with (B) 0.05-10pts.wt. three-stage polymer prepared by polymerizing (B2) 30-70pts.wt. monomer (mixture) consisting of 50-100wt% acrylic acid ester and 0-50wt% another vinyl monomer copolymerizable therewith in the presence of (B1) 10-60pts.wt. (co)polymer obtained by polymerizing 60-100wt% aromatic vinyl compound with 0-40wt% another vinyl monomer copolymerizable therewith to give <=1 reduced viscosity of the resultant homo(co) polymer thereof, and polymerizing 5-30pts.wt. methacrylic acid ester in the presence of (B3) the resultant two-stage polymer prepared in the stages (B1) and (B2) to give 100pts.wt. total components (B1), (B2) and (B3).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a vinyl chloride resin composition, and more specifically, a vinyl chloride resin composition that has excellent mold releasability during molding and provides molded products with good gloss and transparency. The present invention relates to vinyl resin compositions.

[Conventional technology]

Films, sheets, cable coverings, hard products, flooring materials,
Vinyl chloride resin is widely used in the field of textiles and other applications because it has excellent physical and chemical properties.

However, vinyl chloride resin has the disadvantage of poor processability in various ways, and the conventional solution to this problem has been to use a plasticizer, a processing aid such as a copolymer mainly composed of methyl methacrylate, a lubricant, etc. Although this has been done, it has not been a common solution.

Therefore, in order to solve these problems, various research and development efforts have been carried out, and as a result, vinyl chloride resin compositions disclosed in Japanese Patent Publication No. 52-781, Japanese Patent Publication No. 52-3668, etc. Proposed.

[Problem that the invention seeks to solve]

The composition maintains the transparency of the vinyl chloride resin,
The aim is to improve the long-term sustainability of lubricity such as drawdown processability, fluidity during molding, elongation at high temperatures, and release from the roll surface during calendering, and has achieved some results. ing.

However, from the viewpoint of improving productivity, improving quality, and saving energy, there is a need for a processing aid that has long-lasting lubricity when processing vinyl chloride resin, and provides molded products with good gloss and transparency. The above compositions had their limitations. Furthermore, depending on changes in molding processing conditions, an increase in deposits on the mold etc. (plate-out) could be observed, and it could not be said that market demands were fully satisfied.

[Means for solving problems]

An object of the present invention is to solve the above-mentioned problems, and more specifically, it relates to a vinyl chloride resin composition that exhibits excellent mold releasability during molding and provides molded products with good gloss and transparency.

The vinyl chloride resin composition of the present invention comprises: (1) 100 parts by weight of a vinyl chloride (co)polymer in which at least 80% by weight is composed of vinyl chloride units; (u) 60 to 100 parts by weight of an (Al aromatic vinyl compound); weight%
and a polymer or copolymer obtained by polymerizing 0 to 40% by weight of other vinyl monomers that can be copolymerized with this 10 to 6
In the presence of 0 parts by weight, (Bl acrylic ester 50~
Monomer (mixture) 30-7 consisting of 1% 100% by weight and 0-50% by weight of other vinyl monomers copolymerizable with it
0 parts by weight of the reduced viscosity ηsp/C of the polymer or copolymer when polymerized alone (polymer or copolymer 0.1) was dissolved in 100-chloroform, and the solution was dissolved at 25°C.
methacrylic acid ester 5 in the presence of the two-stage polymer obtained in step CA) and step B1 above. ~30 parts by weight, (At, the total amount of each component (B) and (C) is 10
A three-stage polymer obtained by polymerizing to a concentration of 0 parts by weight.
The present invention relates to a vinyl chloride resin composition comprising 0.05 to 10 parts by weight.

Component (1) used in the present invention is a vinyl chloride homopolymer or a copolymer containing 80% by weight or more of vinyl chloride, and examples of the partner monomer of the vinyl chloride copolymer include, for example, acetic acid. Examples include vinyl, propylene, styrene, and acrylic esters. The amount of vinyl chloride resin used is 100 parts by weight.

Next, component (II) used in the present invention is (A).

It is a three-layer structure polymer obtained by sequential polymerization of each component (B) and tc), which imparts lubricity (a styrene polymer and a methacrylic polymer are added to the inside and outside of the Bl component). It has a so-called sand inch structure, which improves cross-mixability with the vinyl chloride resin.

Component (A) is an aromatic vinyl polymer or an aromatic vinyl copolymer containing 40% by weight or less of a vinyl monomer,
As the aromatic vinyl monomer, styrene, α-methylstyrene, etc. are used, and there are no particular limitations on the partner monomer for copolymerization of the aromatic vinyl monomer, and an appropriate monomer can be used depending on the final purpose. Quantities may be used. Examples of such monomers include unsaturated nitriles, vinyl ester acrylic esters, memethacrylic esters, and the like. These may be used alone or in a mixed system of two or more. If the amount of this monomer used exceeds 40% by weight, the synergistic effect between the aromatic vinyl polymer as component A) and the low molecular weight polymer as component (B), such as the persistence of lubricity, may be This is not preferable as it will be extremely low. In addition to such monomers, polyfunctional monomers such as divinylbenzene and allyl methacrylate may also be used. A chain transfer agent such as normal octyl mercaptan may also be used. The amount of the polyfunctional monomer and chain transfer agent used is preferably 2.0% by weight or less.

The blending ratio of component (4) is usually in the range of 10 to 60 parts by weight, preferably in the range of 20 to 5 parts by weight. If the blending ratio exceeds 60 parts by weight, the lubricity will be impaired, and if it is less than 10 parts by weight, the processability will be impaired and the sustainability of the lubricity will be reduced, which is not preferable.

(The Bl component is a polymer made from a monomer selected from acrylic esters or a mixture with other vinyl monomers that can be copolymerized with the acrylic esters. Examples of acrylic esters include ethyl acrylate, butyl acrylate, Examples include benzyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, etc. Other vinyl monomers that can be copolymerized with this include methacrylic esters, acrylic esters, and aromatic vinyl monomers. Examples include styrene, α-methylstyrene, and the like.

Among these, in order to impart good lubricity to the composition of the present invention, it is preferable to use a monomer or monomer mixture that provides a polymer with a low glass transition temperature (as the Bl component). In order to exhibit a more lubricating effect, it is desirable to use a chain transfer agent such as normal octyl mercaptan to lower the molecular weight. /C (0.1 g of polymer or copolymer dissolved in 100 m of chloroform and measured at 25°C) is required to be polymerized so that it is 1.0 or less.Specifically, the chain transfer agent Polymerization is carried out by adjusting the amount of catalyst used, polymerization temperature, etc.

The blending ratio of component (B) is usually in the range of 30 to 70 parts by weight, preferably in the range of 35 to 70 parts by weight. If the blending ratio is less than 30 parts by weight, the lubricity of the resin composition will be impaired, and if it exceeds 70 parts by weight, the surface properties, transparency and gloss will be impaired, which is not preferred.

(Component C1 is a methacrylic acid ester polymer, preferably a polymer made from methyl methacrylate monomer. This is because the methacrylic acid ester polymer has good kneading and mixing properties with the vinyl chloride resin. This is because secondary workability can be effectively imparted.

The blending ratio of this (C1 component) is usually in the range of 5 to 30 parts by weight, preferably in the range of 5 to 25 parts by weight. I am unable to fully demonstrate my sexuality, and (I
I) The polymer tends to cause secondary aggregation in post-processes such as coagulation, dehydration, and drying of the components, which poses a problem in terms of productivity. On the other hand, if the blending amount exceeds 30 parts by weight, the long-term sustainability of the lubricity will be lost, which is undesirable. (II) component is a three-layer structure polymer, and this structure is similar to the above-mentioned (A) and (Easily obtained by sequentially adding and polymerizing each component of C1.

Examples of polymerization methods include emulsion polymerization, suspension polymerization, and bulk polymerization, among which emulsion polymerization is preferred. In the method for producing component (■) using this emulsion polymerization method, in order to form a three-layer structure, polymerization must proceed in the presence of the second and subsequent stages without adding any additional polymerizing agent;
It is desirable to substantially suppress the formation of homopolymers of components (B) and (C). As the emulsifier, any known emulsifier may be used, and for example, common anionic, cationic, or nonionic surfactants can be used. Further, when the pH of the polymerization system becomes alkaline depending on the type of emulsifier used, an appropriate pH adjuster may be used to prevent hydrolysis of the alkyl acrylate ester. As a pH adjuster, boric acid-potassium chloride-sodium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-sodium carbonate, boric acid-sodium carbonate, potassium hydrogen citrate-citric acid, phosphoric acid Potassium dihydrogen-borax, disodium hydrogen phosphate-citric acid, etc. can be used. Further, the polymerization initiator may be a water-soluble, oil-soluble single type or redox type. For example, a water-soluble inorganic initiator such as a normal persulfate may be used alone, or a sulfite, It can also be used as a redox initiator in combination with bisulfite, thiosulfate, etc.

Further examples include redox initiators such as organic hydroperoxide-sodium formaldehyde sulfoxylate, azo compounds, and the like.

Furthermore, in order to impart excellent transparency and sustained lubricity to the composition of the present invention or a molded product thereof in the method for producing a three-layer structure, (BIAvL is present, that is,
Reduced viscosity (ηsp
/C) is 1.0 or less, preferably 0.3 to 0.8. If the reduced viscosity exceeds 1.0, the lubricating effect will be impaired, which is not preferable.

(Even if the reduced viscosity of the C1 component is not particularly regulated, the effects of the present invention will not be impaired. The reduced viscosity of these polymers can be adjusted arbitrarily by conventional methods such as using a chain transfer agent and polymerization temperature. .

The method for producing the vinyl chloride resin composition of the present invention can be achieved by mixing the above-mentioned component (1) and component (II) according to a conventional method.

In addition, the composition of the present invention may contain an organic tin compound,
Stabilizers such as lead-based, barium-based, zinc-based, and other epoxy compounds for metal soaps; lubricants such as stearic acid, ester wax, paraffin wax, and stearyl alcohol; phthalate esters, phosphate esters, and fats.

Potentiating agents such as fatty acid esters and epoxy systems; MBS, AB
Impact-resistant reinforcement agents such as S; coloring agents such as carbon black and titanium oxide; fillers such as calcium carbonate and asbestos; inorganic blowing agents such as ammonia carbonate and sodium bicarbonate; organic blowing agents such as nitro blowing agents and sulfohydrazide blowing agents. , a foaming agent such as an azo foaming agent, etc. may be blended.

The present invention will be further explained in detail below by presenting 8. Examples and Comparative Examples. In addition, all "parts" in the examples are "parts by weight."
shows.

[Embodiments of the invention]

Examples 1 to 3 Two ions of ion-exchanged water were placed in a reaction vessel equipped with a stirrer and a reflux condenser.
After charging 80 parts, 1.5 parts of sodium dioctyl sulfosuccinate, 20 parts of ammonium persulfate, 0.005 parts of n-octyl mercaptan, and (Al component) and purging the inside of the container with nitrogen, the reaction container was heated to 65° C. with stirring. The temperature was raised to ``''C and stirred for 2 hours.
A mixture of 40 parts of -butyl acrylate and 0.5 parts of n-octyl mercaptan was added dropwise over 1 hour, and after the addition was complete, the mixture was stirred for an additional 2 hours. After that, in this reaction system (
A mixture of component C1 and 0.002 parts of n-octyl mercaptan was added over 30 minutes, and stirred for an additional 2 hours.
Polymerization was completed. After cooling the obtained emulsion, it was salted out using aluminum chloride, filtered, washed and dried to produce a polymer.

Next, appropriate amounts of each of the obtained polymers were added to 100 parts of polyvinyl chloride resin (average degree of polymerization 700), 2.0 parts of dibutyltin mercapto, 1.0 part of epoxy auxiliary agent, 0.5 part of dibutyltin malate, and a lubricant. The vinyl chloride resin composition of the present invention was obtained by mixing with 0.3 parts of the above ingredients in a Henschel mixer.

The components of (C) used are collectively shown in Table 1.

In order to demonstrate the remarkable effects of the composition of the present invention, the following evaluation tests were conducted. The results are shown in Table 1.

1. Roll? li: Using 6-inch rolls, kneading was carried out at a roll kneading temperature of 200°C x 195'C, a roll interval of 1 dragon, and a sample of 100P, and after 5 minutes, the peelability from the roll surface was compared. The evaluation is on a 5-point scale, with 5 being the highest peeling, 1 being the lowest peeling, and a value close to 5 indicating culm waste quality. Note that phr is the number of parts of the polymer based on 100 parts of polyvinyl chloride.

2. Same formulation as used for stickiness and lubricity,
Roll mixing temperature 205℃ x 200℃, interval 1, sample 1001 kneading (however, the amount of polymer added is 1.0 phr relative to the vinyl chloride resin) L, the sheet sticks to the roll surface and does not peel off ( The longer this time, the better the durability of slipperiness at high temperatures.

3. Non-gelled material: A sample of the same formulation as used for plate-out two-roll lubricity, the amount of polymer added was 2.0 phr relative to vinyl chloride resin, was kneaded at 180°C x 175°C for 5 minutes, and 0. .3xx sheets were prepared and the presence or absence of ungelled material was determined.

Also, check whether there are any deposits on the roll surface. It was determined that the plate was out.

4. Transparency: Using a sample with the same formulation as that used for roll slippage, with the amount of polymer added being 0.5 phr relative to the vinyl chloride resin, the sample was kneaded for 5 minutes and then press-pressed at 185°C. After creating a press plate with a thickness of 2u, it was measured using an integrating sphere haze meter (according to JIS-6714).

5. Gloss: A sample was mixed for 5 minutes using the same formulation as the one used to evaluate roll slipperiness, and the amount of polymer added was 0.5 phr relative to the vinyl chloride resin. , a press plate with a thickness of 2 m was prepared and then visually judged.

Comparative Example 1 As shown in Table 1, (B) in Example 1
After reacting the component as the first component of this comparative example, 150 parts of methyl methacrylate (component C1) and 2 parts of n-octyl mercaptan 00OO were added and polymerized in the same manner as in Example 1 to form a polymer. (Two-stage polymer without component (4) in Example 1) was produced.

Next, an appropriate amount of the obtained polymer was added to polyvinyl chloride resin (
Average degree of polymerization 700) 100 parts, dibutyltin mercap) 2
, 0 parts of epoxy auxiliary, 0.5 parts of dibutyltin malate, and 0.3 parts of lubricant in a Henschel mixer to obtain a composition. The results are shown in Table 1.

Comparative Example 2 In the reaction vessel used in Example 1, a mixture of 280 parts of ion-exchanged water, 1.5 parts of dioctyl sodium sulfosuccinate, 2.0 parts of ammonium persulfate, 50 parts of styrene as a prisoner component, and parts of n-octyl mercaptan o and oos was added. After the inside of the container was replaced with nitrogen, the temperature of the reaction container was raised to 65° C. under stirring, and the mixture was heated and stirred for 2 hours. Next, under the same conditions as Example 1 (
50 parts of butyl acrylate (Bl component) was reacted, and a polymer (a two-stage polymer without component (C)) was produced in the same manner as in Example 1.

Next, an appropriate amount of the obtained polymer was added to polyvinyl chloride resin (
Average degree of polymerization 700) 100 parts, dibutyltin mercap) 2
, 1.0 part of epoxy auxiliary agent, 0.5 part of diptyltin malate, and 0.3 part of lubricant in a Henschel mixer to obtain a composition. The results are shown in Table 1.

Comparative Example 3 A composition was obtained in the same manner as Comparative Example 1 except that no polymer was used. The results are shown in Table 1.

Examples 4 to 6 Vinyl chloride resin compositions of the present invention were obtained in the same manner as Examples 1 to 3, except that the components of (AJ to (C)) used are shown in Table 2.Results are shown in Table 2.

Comparative Examples 4 to 6 Compositions were obtained in the same manner as Examples 1 to 3, except that each component shown in Table 2 was used. The results are shown in Table 2.

Examples 7 to 9 Vinyl chloride resin compositions of the present invention were obtained in the same manner as Examples 1 to 3, except that the components of (C) to (C) used are shown in Table 3. The results are shown in Table 3.

Comparative Examples 7-8 Compositions were obtained in the same manner as Examples 1-3, except that each component shown in Table 3 was used. The results are shown in Table 3.

〔Effect of the invention〕

As detailed above, the vinyl chloride resin composition of the present invention has much better processing characteristics during molding than conventional ones, and molded products obtained from the composition have good transparency. Its industrial value is extremely limited.

Claims (1)

Scope of Claims: (I) 100 parts by weight of a vinyl chloride (co)polymer of which at least 80% by weight is composed of vinyl chloride units; (II) 60 to 100% by weight of (A) an aromatic vinyl compound; In the presence of 10 to 60 parts by weight of a (co)polymer obtained by polymerizing 0 to 40 parts by weight of another vinyl monomer that can be copolymerized with (B) 50 to 100 parts by weight of acrylic ester and this Reduced viscosity ηsp/C of the (co)polymer when 30 to 70 parts by weight of a monomer (mixture) consisting of 0 to 50% by weight of other vinyl monomers that can be copolymerized with these are solely polymerized.
(0.1 g of (co)polymer dissolved in 100 ml of chloroform and measured at 25°C) was polymerized to obtain a copolymer of 1.0 or less, and (C) the above step (A) and In the presence of the two-stage polymer obtained in step (B), 5 to 30 parts by weight of methacrylic acid ester is added until the total amount of each component of (A), (B) and (C) is 100.
Three-stage polymer obtained by polymerizing so that the weight part is 0.0
A vinyl chloride resin composition comprising 5 to 10 parts by weight.