JPS6162547A - Vinyl chloride resin composition and its production - Google Patents

Abstract

PURPOSE:The titled composition that is obtained by polymerizing vinyl chloride monomer in the presence of a specifically composed polyester resin from lactone, diol, and aromatic dicarboxylic acid, thus giving formed products with high migration resistance under high temperature and humidity and with high thermal aging resistance. CONSTITUTION:The objective composition is composed of (A) 100pts.wt. of a vinyl chloride resin and (B) 20-120pts.wt. of a polyester resin which has a polycondensation composition of 69-90mol% of a lactone, preferably epsilon- carpolactone or a hydroxycarboxylic acid such as 6-hydroxycaroic acid, 17.5-5mol% of diol, preferably neopentyl glycol and 17.5-5mol% of aromatic dicarboxylic acid, preferably isophthalic acid, and an average molecular weight of more than 10,000 and less than 20 hydroxyl value. It is obtained by radical polymerization of vinyl chloride or a mixture thereof with copolymerizable monomers in the presence of the polyester resin of component B.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention has excellent so-called non-migration properties in which the plasticizer does not migrate from the inside of the molded product even under conditions of crystal mud and high humidity, and has heat aging resistance. The present invention relates to a vinyl chloride resin composition that can give molded articles.

"Prior Art" Polyvinyl chloride can have its physical properties changed over a very wide range by adding a plasticizer, and is widely used industrially as a thermoplastic resin suitable for various hammer applications. As plasticizers for polyvinyl chloride, fatty acid esters such as phthalic acid esters, including dioctyl phthalate, and dioctyl adipate are the most common because of their excellent plasticizing efficiency. However, these plasticizers have a tendency to migrate from the inside of the molded product to the surface, and molded products containing these plasticizers do not suffer from deterioration of physical properties due to a decrease in plasticizer over time, but rather are If one resin molded product is brought into contact with another resin molded product for a long time, the plasticizer will migrate to other resin molded products, causing alteration and deterioration of the resin molded product. For the purpose of non-migration, attempts have been made to use trimellitic acid ester plasticizers or liquid polyester plasticizers obtained by reacting adipic acid with ethylene glycol and/or 3-butanediol, or in combination. Although the migration property is improved to some extent, depending on various conditions, for example, in a high temperature and high humidity environment, complete non-migration and plasticization efficiency are significantly inferior to those mentioned above, and it is difficult to achieve the same level of plasticization efficiency. In order to obtain such plasticizer, a large amount of expensive material must be used, which is not only disadvantageous in terms of cost, but also causes other undesirable effects due to the large amount of plasticizer added to the obtained molded product. It cannot be used as a general-purpose plasticizer.

In order to prevent plasticizer migration, flexible polymeric compounds are used to plasticize vinyl chloride resins, such as ethylene-vinyl acetate copolymer, ethylene-oxygen oxide-vinyl acetate copolymer, thermoplastic polyurethane, and NBR. , attempts have been made to blend polycaprolactone, etc. into vinyl chloride resin, but these polymer compounds are not simply blended or mixed.
Even if such a vinyl chloride resin composition can be manufactured, lumps due to polymer compounds that are incompatible with the vinyl chloride resin may occur in molded products manufactured using it. , which appear as so-called "pockets" on the surface of the molded product, causing the surface of the molded product to become rough and the strength of the molded product to be weakened.

Even if the vinyl chloride resin composition is sculpted using the above-mentioned polymer compound, the liquid plasticizer may be slightly susceptible to migration, but molded products manufactured from the composition may When resin molded products come into contact with each other in a harsh environment of high temperature and humidity, the surface of other resin molded products becomes contaminated with plume from the molded products, resulting in a phenomenon similar to liquid plasticizer migration (hereinafter also referred to as "this phenomenon"). (referred to as "transition") occurred, and it was not possible to completely avoid migration.

In addition, in recent years, a new liquid polyester plasticizer containing lactone, diol, and dicarboxylic acid as main reaction components, which can be used as a plasticizer for vinyl chloride resin, has been developed, for example, in JP-A-Shoj.
/-/Kutako r publication, same j/-11 go 4to publication and same! /-j[,<(7/publication lid K) However, all of these polyester plasticizers have average molecular weights in the range of roo to /da0θ, and even if this polyester plasticizer is Even if the salt is blended and kneaded with a hibinyl-based resin, the resulting composition exhibits large migration properties, similar to those using conventional liquid plasticizers, and it is difficult to expect excellent non-migration properties. A similar technology is disclosed in JP-A-37
-/≦A polyester polyol resin with a melting point of 20°C or less synthesized from a polyhydric alcohol, a polybasic acid, and -monocaprolactone disclosed in Publication No. It shows that it is possible. However, the hydroxyl value of these resins are all! ! This value indicates that the resin has a low molecular weight. Even if this is mixed with vinyl chloride resin, it has poor compatibility with vinyl chloride resin and bleeds because it is a vinyl chloride resin composition, and sufficient non-migration properties cannot be expected. In addition, JP-A-Shoj9-10♂0j
-2 publication describes a molecule Q/
A vinyl chloride resin composition is disclosed in which a polyester polyol block copolymer of 4000100.00θ is mixed with a vinyl chloride resin. The polyester obtained from this diol and aliphatic dicarboxylic acid has a substantial K
N-type polyester diol is used, and the polyester polyol obtained by reacting this with lactone has high crystallinity and is not sufficiently compatible with vinyl chloride resin, so it cannot give good strength to the molded product. It becomes difficult.

"Problems to be Solved by the Invention" 1. The present inventors have developed the above-mentioned conventional technology t! - In view of this, in order to obtain a vinyl chloride resin composition that has excellent non-migration properties and heat aging resistance even under high temperature and high humidity conditions, we investigated the conditions for various plasticizers. The material that should become the agent (quality, that is, the plasticized material has a high molecular weight,
It is open and flexible at room temperature, and its flexibility can be maintained even by adding vinyl chloride resin. Secondly, the plasticized product has low crystallinity, there is no vinyl chloride bleed, and the hardness of the resin composition does not change. We assumed that conditions such as no plasticity were required, and judged that an amorphous polyester with a low hydroxyl value would be suitable as a plasticized product that met these conditions, and selected a polyester with a specific structure and specific physical properties. As a result, they found that the polyester is most suitable for achieving the object of the present invention, and furthermore, they found that the polyester can be processed well without adhering to the walls of a mixing machine or the like when mixed with a salt-based resin. This discovery led to the completion of the present invention.

That is, an object of the present invention is to provide a molded product which has excellent so-called non-migration properties, without migration of plasticizer (plasticized product) from internal forces of the molded product even under harsh environments of high temperature and humidity, and has heat aging resistance. Provided is a chlorinated beer resin composition capable of providing

"Means for Solving the Problems" The gist of the present invention is that vinyl chloride resin/θ' M fk part and polyester resin, 20 to 1
70 weight parts Δ), wherein the polyester resin is a lactone or an oxyacid 6! ~90 molar width, 17.5 to 5 molar diols and aromatic dicarboxylic acids/
7. j~! The present invention relates to a vinyl chloride resin composition having a polycondensation composition of molar ratio, a number average molecular weight IQ of 000 or more, and a hydroxyl value of 20 or less.

The present invention will be described in detail.

As the vinyl chloride resin used in the composition of the present invention, vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith can be prepared by a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method, or an emulsion polymerization method. All products manufactured by this method can be used. Polymerization may be carried out in the presence of a polyester resin described below. Therefore, examples of comonomers that can be copolymerized with vinyl chloride include vinyl acetate, vinyl propionate, acrylic acids such as vinyl acetate, vinyl propionate, vinyl gamma acrylate, ethyl acrylate, butyl acrylate, etc. Esters, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, maleic acid esters such as dibutyl maleate and diethyl maleate, heptamalic acid esters such as dibutyl 7-maleate and diethyl fumarate, vinylmethylnythyl, vinyl Vinyl ethers such as butyl ether and vinyl octyl ether, cyanide vinyls such as acrylonitrile and methacrylaterile, α-olefins such as ethylene, flopylene, and styrene, salt f
Examples of halogen halogens other than vinyl chloride, such as hypinylidene and vinyl chloride, include vinyl halides, and these comonomers are preferably 30 or less, preferably 20 or Used in the range of excellent and below. Of course, the comonomers are not limited to those mentioned above.

The polyester resin, which is component -1 of the present invention, has a polycondensation power consisting of lactone or its corresponding oxyacid, diol, and aromatic dicarbonate, each of which is ≦90 mol%, 17J-6 Mol% and 17
．． j-1 mol% composition ratio), the number average molecular weight measured by G, P, and O of the polyester resin is 1
in the range of 0,000 to 100,000, preferably IC4
000～! In the range of 40θ0 and J Engineering S K 007
The hydroxyl value measured by 0 is 20 or less, preferably!
It must be in the range ~/j. The ratio of diol and aromatic dicarboxylic acid is preferably substantially equimolar. Lactone or its corresponding oxy@(
If the composition ratio of lactone (hereinafter simply referred to as "lactone") is less than ≦j mol%, the stickiness of the polyester resin will increase, and the stickiness cannot be removed even by adding vinyl chloride resin, and the compounding machine It is difficult to handle the vinyl chloride resin composition because it adheres to the machine wall of the crosstalk machine or the calender roll, etc., and it exhibits excellent non-migration properties under high temperature and humidity conditions, regardless of the molecular weight of the polyester resin. If this happens, the crystallinity of the polyester resin due to lactone increases, which tends to impede compatibility with the vinyl chloride resin, resulting in problems such as changes in hardness of the vinyl chloride resin composition over time. The effect of lactones on crystallinity can be significantly reduced by selecting diols or aromatic dicarboxylic acids that are chemically asymmetric. Therefore, the lactone is not particularly limited as long as it can be ring-opened and copolycondensed easily, but for example, -1-propiolactone, α-methyl-β-propiolactone, α, α -dimethyl-β-propyl second chthone,
β-methyl-β-propiolactone, α-ethyl-β-
Propiolactone, piparolactone, δ-valerolactone, e-caprolactone, methyl-1-caprolactone, dimethyl-ε-caprolactone, trimethyl-C-caprolactone, etc., include s''* ring, 6-membered ring, and 7-membered ring. is preferable because it undergoes ring-opening polymerization easily.Also, it is most preferable to use e-caprolactone because it is easily available industrially.Also, as the oxyacid, one having a carbon thickness corresponding to the above-mentioned lactone can be used. For example, e-hydroxycaproic acid is suitable.

As the diol, any diol that can be used as a raw material for conventional polyester plasticizers can be used. For example, ethylene glycol, diethylene glycol, /,! -7'
Ropanediol, comethylpropanediol, /, -
Monobutanediol, /, 3-butanediol%/, goobutanediol, /,! -bentanediol, hexanediol, neopentyl glycol, etc.
1. Gold is used alone or in combination of two or more of these. Compatibility of polyester resin with vinyl chloride resin,
Considering the flexibility of the vinyl chloride resin composition, neopentyl glycol is particularly preferred.

Examples of aromatic dicarboxylic acids include heptallic acid (including thalene dicarboxylic acid, diphenyl dicarboxylic acid, bis(carboxyphenyl)methane, ethylenebisbenzoic α, anthracene dicarboxylic acid, etc.), and at least seven of these are used. Among these, for the purpose of increasing the flexibility of the polyester resin, aromatic dicarboxylic acids that are asymmetric in chemical structure, such as inphthalic acid, khunaphthalic acid, and 7-su7tale dicarboxylic acid, are preferable. In particular, when considering ease of industrial availability, compatibility of the produced polyester resin with vinyl chloride resin, plasticization efficiency, etc., isophthalic acid is most preferable.

In addition, the number average molecular weight of the polyester resin is 70.000
If it is smaller, the non-migration resistance in a hot and humid environment will not be sufficient, and it will also tend to adhere to blenders, mixers, calender rolls, etc., making it difficult to obtain a composition that satisfies all physical properties. On the other hand, when the value increases by 10 (2000), the ability to plasticize vinyl chloride resin decreases.1-1
The crosstalk with the vinyl chloride resin is insufficient, and the processing of the composition is likely to be hindered. If the water α crystallization of the polyester resin is larger than 20, it means that the polyester resin itself has many free hydroxyl groups or has a small molecular weight, and the transfer of the polyester resin from the salt 1-hibinyl resin composition becomes easy. , resulting in KM oxide hardening over time.

Further, the polyester resin used in the present invention is preferably a random copolymer as well as a block copolymer of the above-mentioned constituent components. Block copolymers have high lactone crystallinity and tend to have poor compatibility with vinyl chloride resins, causing migration phenomena and having a negative impact on the strength of molded products when stored in hot and humid environments. Easy to give.

Therefore, the composition of salt (and vinyl resin and polyester) is determined by the type of lactone in the polyester resin,
Although it varies depending on the mol% of lactone content, the polymerization of the salt f vinyl resin, the plasticity ratio of the vinyl chloride resin, and the vinyl chloride, the former is usually 100%.
The latter is 20% by weight. It may be determined as appropriate from the range of -120 parts by weight.

If the polyester resin is less than 20 parts by weight, it is difficult to make a composition made of plasticized vinyl chloride resin, and if it is more than -5720 parts by weight, the vinyl chloride resin cannot be used in processing equipment such as crosstalk machines and calender rolls. The adhesive strength of the composition increases, and processing 4! l! The composition easily adheres to the container,
Moreover, the operability is deteriorated.

In order to produce the vinyl chloride resin composition of the present invention, the Shunshu method can be adopted. For example (1)
After radical polymerization of vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith in the presence of a polyester resin, the vinyl chloride resin composition is separated and dried.

(2) After mixing the vinyl chloride stool latex and the polyester resin latex, the vinyl chloride resin composition is separated from the latex by a method such as salting out or spray drying.

(3) The dissolved polyester resin is gradually absorbed into the heated vinyl chloride resin and then mixed uniformly to form a vinyl chloride resin composition.

(4) Mix vinyl chloride resin and polyester resin,
A basic vinyl resin composition is obtained by heating and mixing.

Examples of methods include: Among these manufacturing methods, method (1) is the most excellent in achieving good gelling properties of the composition.

Predetermined amounts of water, polymerization catalyst, and polyester resin are charged, and after degassing under reduced pressure, vinyl chloride is press-ined, and the polyester resin is dissolved in vinyl chloride with stirring at room temperature or under heating. Warm it up to start the polymerization reaction. After the reaction is completed, unreacted vinyl chloride is removed, and the vinyl chloride resin composition is dried for 1 minute by a conventional method. Completed between polyester. Further, as the polymerization catalyst and suspension stabilizer, those used in ordinary suspension polymerization can be used as they are. Of course, this specific method can also be employed in the emulsion polymerization method and the suspended fIA polymerization method.

The above-mentioned method (2) for producing the composition of the present invention includes, for example, producing latex by emulsifying and dispersing polyester resin in the production process, or producing polyester resin in an aqueous medium in the presence of a surfactant at a melting point of Polyester resin latex is produced by heating and melting at the above temperature while stirring, and is then play-dried to obtain a vinyl chloride resin composition. Examples of surfactants include, but are not limited to, higher fatty acid salts, alkyl sulfur ester salts, alkylbenzene sulfone squares, sulfosuccinic acid dialkyl ester salts, Sorubikun high M 1m fat city ester, and Ikeso's polyoxy7-ethylene derivatives. is used as appropriate.

LrIm of the present invention
, tu'F+-Bo IJ ester resin, it may contain stabilizers, ultraviolet absorbers 1 colorants, foaming agents, crosslinking agents, fillers, etc. as necessary. ``Effects of the Invention'' The vinyl chloride resin composition of the present invention is a polyester resin having a specific composition with a number average molecule of 2,000 or more and a hydroxyl value of θ or less, which is composed of a diol containing lactone as a main component and an aromatic dicarbonate. Because it is used as a plasticizer or softener for vinyl resins, there is no migration even when molded products made from the composition come into contact with other resin molded products or under hot and humid snowpack. Furthermore, since it does not contain a low-molecular-weight plasticizer, phenomena such as the release of the W softening agent do not occur, and therefore, no change in the hardness of the molded product over time is observed.
llrl Heat aging properties are also good. In addition, no matter how the composition of the present invention is manufactured or what processing method is used, it is important to note that no matter what method is used to manufacture the composition of the present invention, no matter what processing method is used, the manufacturing machine, mixer, mixer, calender roll, etc. will not contain polyester resin or chloride. There is no adhesion of the vinyl resin composition, and it has excellent operability and workmanship. Therefore, the composition of the present invention has high utility value as a material for automobile interior materials, medical films or tubes, packing, electric wire coatings, and the like.

"Examples" Next, the vinyl chloride resin composition of the present invention will be explained in detail in Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

The gelling properties, migration properties, and heat aging resistance of the vinyl chloride resin compositions obtained in each Example and Comparative Example were evaluated by the following methods, and the results are shown in Tables 1 and 1. .

Fogling property> A lubricant, a filler, and a stabilizer are added to and mixed with a vinyl chloride resin composition, mixed with a roll at 740°C, and then the roll gap is set to σ.
, cut out a part of the sheet at regular intervals, and reduce its lIr to 740"Cl00 under the condition of 9/aA.
It was pressed for a minute to obtain a pressed film.

The quality of gelatinization was determined by counting the total number of spots in this film.

Migration property> A lubricant, a stabilizer, and a filler were added to the vinyl chloride resin composition, and the mixture was mixed with a roll at 140°C for 1 minute to obtain a sheet with a thickness of approximately q-sa). Stack multiple sheets and heat to 140℃
, under the conditions of 100kg/cI/l! It was pressed for a minute to form a sheet with a thickness of 3M.

A test piece with a width of 0m and a length of jOm was cut out from this press sheet, and its transferability was evaluated under dry and wet conditions.

The evaluation criteria were as follows: ◎ indicates that no change was observed in the surface condition when visually observed, and grades of ◎, ∆, and × are given from Ja to best.

Dry conditions: The test piece was stacked on each of polystyrene (polystyrene), ABEI sheet, and metallic painted sheet, sandwiched between glass plates, and left open for 7 days at 60°C under a load of 3009, and then peeled. 1 Wet conditions: Temperature? After leaving the test piece alone for 72 days in an open air conditioned at θ°C and humidity of 90%, the test piece was taken out, and the test piece was further tested in the same manner as under dry conditions. The surface condition of each painted sheet was examined.

Heat Aging Resistance> Layer sheets of approximately o, t, j)- prepared for migration test at 760℃ and 100kg/crll! Pressing was carried out for a minute to obtain a pressed sheet having a thickness of /III.

The residual tensile strength and residual elongation of the sheet were determined in accordance with the post-heating tensile test of J.K. SK 47uj.

However, the heating conditions for the sheet were 120°C, which was stricter than the prescribed heating temperature.

Example/ Stainless steel autoclave with internal volume of 3 tons containing deionized water jjir, ε-caprolacket/θ
Mole Yu, neopentyl glycol 10 moles and isophthall! Number average molecular weight 2L obtained by copolycondensation of 10 mol% of I2: 2θ00° hydroxyl value/j polyester resin/70 pr to sorbitan monolaurate/1
r1 lauroyl peroxide j,/jir and polymerization initiation retardant 3. ! - After charging ditertiary butyl derhydroxytoluene 0.0/7 Er,
Degas the autoclave and place vinyl chloride tFO in it.
9r was introduced. Next, the temperature of the autoclave was raised to 9.degree. C., and stirring was continued at this temperature for 7 hours to dissolve the polyester resin in vinyl chloride.

Thereafter, 77θlr of deionized water containing partial saponity polyvinyl acetate, -jlr was injected, and the temperature was raised to 60°C, at which point polymerization of vinyl chloride was initiated. After continuing the polymerization until the pressure within the polymerization system showed a drop of 2 kg/aA, unreacted vinyl chloride was collected and the reaction was terminated. The reaction polymer was dehydrated and dried to obtain a resin composition. The reaction time required 30 minutes.

The obtained vinyl chloride resin composition is polyester resin 2.
Contains 3'x amount, average particle size 306N, 2 Example/The amount of polyester resin used in Example/ is increased to 3001r, and vinyl chloride! Vinyl chloride was polymerized in the same manner as in Example, except that the amount was reduced to JO9r, to obtain a white powdery salt resin composition containing polyester resin Dada weight coefficient and having an average particle size of 330μ. The time required for the reaction was da hours.

Example 3 A polyester resin cog, Halacroyl haloxide 4t9011r1, was directly used in a glass-lined polymerization can with an internal volume of 300t and 77kf of deionized water and a running column.
After adding a polymerization initiation retardant/gPR and degassing the inside of the polymerization reactor, apply a salt f hibinyl lamp.

After stirring at a temperature of 4 to ℃ for 2 hours and dissolving 1 polyester resin in vinyl chloride, partially
7 kg of deionized water containing R was injected and polymerization was carried out at a temperature of 61 °C. After continuing the polymerization until a pressure drop of 1 kg/car was shown, unreacted vinyl chloride was recovered. A polymer was obtained by dehydration and drying.This polymerization method was used to reduce polyester resin q4 to an average particle size of 2
3? μ, it was a white powder vinyl chloride resin composition.

Pour deionized water into a stainless steel autoclave with a capacity of 3 tons. llr, same polyester resin as used in implementation side/30θF rs polymerization inhibitor Q, 0
/7 After charging Ir, the interior of the autoclave was degassed, and the salt f-hibinyl 6♂09r was introduced into it. Next, the temperature was externally heated to 4 to C, and stirring was continued at this temperature for 7 hours to dissolve the polyester resin into the vinyl wall.

After that, di-secondary butyl peroxydicarbonate θ, rjgr was injected, then dipropyl methylcellulose in hydrochloride/deionized water containing 7jlr 7701
7r was press-fitted. The temperature was further raised to Krr°C, and at this temperature, the pressure in the polymerization system was reduced to 90°C, and ml of salt 1-hibinyl was recovered and dehydrated and dried to obtain a polymer. The reaction time was da hours. The average particle size of this polymer is /! ≦μ, the content of polyester resin was lr weight t%.

Implementation queue! Contents Deionized water θθ1 in a glass container of FIIjt
r, polyester resin 3007/r used in Jyugyo Misaki/
After charging, the temperature was raised to 70°C to melt the resin. Next, deionized water J0θyr ta containing myristicin (li411r and ammonia 3ir (ammonia water was used for 214) was pressed into the mixture to obtain a polyester resin latex.

To the latex, a latex/4tθ01r containing salted vinyl resin 3λ weight having a nine-average particle diameter of 0.3μ, which was separately prepared by emulsion polymerization, was added to form a homogeneous mixture KL, and this mixed latex was destroyed with dilute hydrochloric acid while stirring. The precipitated polymer was washed with water, dehydrated, and dried to obtain a salt f-hibinyl resin composition uniformly containing 90% by weight of polyester resin.

Example 6 A vinyl chloride resin j It9 with an average degree of polymerization (p) / j Oθ produced by suspension polymerization was charged into a lipon blender with an internal volume of θt, heated to 70°C, and then heated separately to 90°C. 1 kg of the polyester resin used in Example 1 was melted at
After the addition, the temperature was further increased to 710°C to uniformly absorb the polyester resin into the vinyl chloride resin, and after cooling, a vinyl chloride resin composition containing a weight percent polyester resin was taken out. Equipment for melting polyester resin! (:4000~414000
cpe (B-type viscometer, 7.0 rotations). ``Furthermore, almost no adhesion of the polyester resin and vinyl chloride lubricant composition was observed on the inner wall of the ribbon blender.

(Deposition 101/r).

Comparative Example/ In Example 1, polymerization was carried out in the same manner as in Example 1, except that the polyester resin was replaced with polycaprolactone.
Average particle diameter containing 6% by weight of polycaprolough tongs!
A vinyl chloride resin composition of JrOμ was obtained. The polymerization took 20 minutes.

Comparative Example λ Polyester resin ts' used in Example f11-
- Replaced with polyester obtained by copolycondensing caprolactone gQ mol%, neopentyl glycol 20 mol, and isophthalic acid 0 mol %, implementation fp, 2
Polymerization was carried out in the same manner as in Example 6 to obtain a vinyl chloride resin composition containing 41j% by weight of polyester and having an average particle size of 4110μ.

The reaction took 70 minutes.

The samples that were exposed to a high temperature and humidity environment, that is, kept in a wet state and then subjected to a migration test, were slightly inferior to the dry samples in the examples. However, in the case of the comparative example in which only polycaprolactone was used as a softener, it was carefully confirmed whether this was due to poor compatibility of polycaprolactone with vinyl chloride resin, hydrolysis, or high crystallization. However, the transferability test results were poor. In Comparative Example 1, the content of ε-caprolactone in the composition of the polyester resin was low, and when the rolls were crossed, the material adhered to the rolls significantly, and a sheet for preparing a test piece could not be obtained.

In addition, if the gelling property test shows a value of around 10 after 7 minutes of crosstalk, it is sufficient for practical use. Implementation f11! Although the method for producing the composition is easier than the method of polymerizing vinyl chloride in the presence of polyvarnish resin, it still shows a considerably high value after 7 minutes of crosstalk, and a slightly longer crosstalk time is required. It takes.

Comparative Examples 3 to 6 @-2 After uniformly mixing vinyl chloride resin compositions having the compositions shown in Table 2, a film with a thickness of approximately θ was created by cross-rolling, and a press sheet was created from the film, and then a test piece was prepared. The sample was cut out and subjected to migration test and heat aging resistance test, and the results are listed in Table 1.

Comparative example and! As is clear from the above, those using thermoplastic polyurethane and a liquid conventional polyester plasticizer had poor migration properties at a high temperature of 784t, and as in Comparative Example 3, those using NER The product was heat resistant [XWf with poor L properties. In the case of a ratio of 132, the ethylene-carbon-vinyl acetate copolymer did not form a flexible sheet even when 7i-200 parts of the copolymer was added.

Patent Applicant Mitsubishi Monsanto Plastic Vinyl Co., Ltd. Agent Patent Attorney Probability - 7 others Procedural Amendment/Indication of Case 1954 Patent Application No. tlulJO No. 3
Title of the invention Vinyl chloride resin composition and its manufacturing method J Relationship with the case of the person making the amendment Name of patent applicant Title Mitsubishi Monsanto Plastic Vinyl Co., Ltd. Attorney 2-chome J, S, Marunouchi, Chiyoda-ku, Tokyo 100 Order for amendment Date of (voluntary) Mu Number of inventions to be increased by amendment O ri Target of amendment Detailed description of invention column (2) of the same page 6, bottom line "r/o, θOθ" riL: 2θQθ~ ” is corrected.

(3) In the 5th line of page 1tI, the words "increase flexibility" are corrected to "reduce crystallinity."

that's all

Claims (5)

[Claims] (1) A composition comprising 100 parts by weight of a vinyl chloride resin and 20 to 120 parts by weight of a polyester resin, wherein the polyester resin contains 69 to 90 parts by weight of a lactone or an oxyacid.
mol%, has a polycondensation composition of 17.5 to 5 mol% of diol and 17.5 to 5 mol% of aromatic dicarboxylic acid, and has the properties of a number average molecular weight of 10,000 or more and a hydroxyl value of 20 or less. A vinyl chloride resin composition characterized by the following. (2) The vinyl chloride resin composition according to claim 1, wherein the lactone is ε-caprolactone or 6-hydroxycaproic acid. (3) The vinyl chloride resin composition according to claim 1, wherein the diol is neopentyl glycol. (4) The vinyl chloride resin composition according to claim 1, wherein the aromatic dicarboxylic acid is isophthalic acid. (5) lactone or oxyacid 65-90 mol%, diol 17.5-5 mol% and aromatic dicarboxylic acid 17.
5 to 5 mol% polycondensate with a number average molecular weight of 10,
A method for producing a vinyl chloride resin composition, which comprises polymerizing vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith in the presence of a polyester resin having a property of 000 or more and a hydroxyl value of 20 or less.