JPS59191750A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide a vinyl chloride resin compsn. having excellent thermal stability and processability, a homogeneous surface and excellent matte effect, consisting of a vinyl chloride copolymer contg. polyethylene glycol di(meth)acrylate and a vinyl chloride copolymer contg. diallyl phthalate. CONSTITUTION:A compsn. consists of 50-90wt% vinyl chloride copolymer (A) composed of 97.0-99.95wt% vinyl chloride and 3.0-0.05wt% polyethylene glycol diacrylate or dimethacrylate having the number of ethylene glycol polymerized units of 4-50 and 50-10wt% vinyl chloride copolymer (B) composed of 99.0-99.95wt% vinyl chloride and 1.0-0.05wt% diallyl phthalate. Part of vinyl chloride in copolymer A may be replaced with other vinyl monomer such as vinylidene chloride, vinyl acetate, ethylene or propylene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved FC vinyl chloride resin, and more specifically to a hard, semi-118 resin that exhibits a faded surface of a molded product.
j! This invention relates to a soft vinyl chloride resin composition.

Due to its excellent properties, vinyl chloride-based clear resin is used in a wide variety of applications ranging from hard, semi-hard to soft, but recently matte products have been used in areas such as building materials, furniture materials, and automobile interior and exterior parts. Demand has increased, and conventional vinyl chloride resins with good surface gloss are no longer able to satisfy these demands.

There are methods to make the entire surface of a vinyl chloride resin molded product matte, such as adding fillers, applying matte paint, and secondary surface processing, but these methods lead to a decrease in physical properties, a decrease in productivity, and a high cost. There are problems such as an increase in Furthermore, methods have been proposed to obtain resins that give matte molded products by combining vinyl chloride with other unsaturated compounds. For example, Copolymer (Japanese Unexamined Patent Publication No. 56-5843), ■ Copolymer with chlorinated diacryl phthalate (%
-163939). However, these methods still have drawbacks. For example, the resin obtained by method (■) has an insufficient degree of matteness, has poorer thermal stability than general polyvinyl chloride resin, and tends to be slightly yellowed in hard or semi-hard molded products. It will be done. In addition, the resin obtained by the method (2) has a non-uniform surface with many irregularities, a high melt viscosity, and poor processability.

The present invention was made in view of the above circumstances, and
The purpose is to provide a vinyl chloride thread resin composition that has excellent thermal stability and processability, and can yield hard, semi-hard or soft molded products with a homogeneous surface and excellent matte effect. Another object of the invention is to provide a hard, semi-hard or soft polyvinyl chloride molded product with a uniform surface and excellent matte effect. That is, the present invention consists of 97.0 to 99.95% by weight of vinyl chloride and 3.0 to 0.05ffii% of polyethylene glycol diacrylate or polyethylene glycol dimethacrylate in which the number of polymerized units of ethylene glycol is 4 to 5o. Vinyl chloride copolymer (A) 50 to 90% by weight, and vinyl chloride copolymer (B) consisting of 99.0 to 99.95% by weight of vinyl chloride and 1.0 to 0.05xitts of diacrylphthalate. Vinyl chloride yarn 1 is characterized by comprising 50 to 1% ON (a fatty acid compound).The structure and effects of the present invention will be explained in more detail below.

Vinyl chloride yarn copolymer (A): The vinyl chloride yarn copolymer (A) used in the present invention is a vinyl chloride monomer (hereinafter referred to as V
(sometimes referred to as OMR) 97.0 to diester with acid or methacrylic acid (hereinafter referred to collectively as PEGD)
(sometimes abbreviated as Fi) 3.0 to 0.051 [f%
It is a copolymer obtained by copolymerizing the following.

In the copolymer (A), a part of VOMR can be replaced with another vinyl monomer as long as the object of the present invention is not impaired. Examples of such other vinyl monomers include vinylide chloride/vinyl acetate, methyl vinyl ether, ethylene, propylene, etc., and the amount to be replaced is the vinyl chloride component in the copolymer (A). is in the range of 50% by weight or more, preferably 7ON amount or more.

In the vinyl chloride copolymer (A), PEGI)E
may be polyethylene glycol diacrylate (hereinafter referred to as PKGA), polyethylene glycol dimethacrylate (hereinafter referred to as PFiGM), or a mixture of both in any ratio, and furthermore, polyethylene glycol and any ratio in any ratio. A mixed ester obtained from a mixture of acrylic acid and methacrylic acid may also be used. In these PEGI)E, if the number of polymerized units of ethylene glycol in the polyethylene glycol portion is 3 or less, the matting effect of the molded product is insufficient, and if it exceeds 50, efficient copolymerization becomes difficult, and unpolymerized PICGDI! !
This is undesirable because it blooms out on the surface of the final molded product.

Even if the ratio of PFiGDE in the copolymer (A) exceeds 3.0%, the eradication property will not be improved. PffGDE that does not remain during coalescence or has a very small amount remaining is difficult to prepare by normal polymerization methods, and historically the yield during polymerization is extremely low, making it economically unpractical. . Moreover, if the ratio is less than 0.05% by weight, the erasing effect of the molded product will be poor.

As a method for producing the vinyl chloride yarn co-fused composite (A), any known method used for polymerizing vinyl chloride can be used. That is, any of the following methods may be used: bulk polymerization, @turbid polymerization, emulsion polymerization, and solution polymerization using a decomposed peroxide as a polymerization initiator. However, unless there are other problems, good reproducibility of polymerization rate, 1 degree, etc., and easy process control! @ 1 cup of turbidity is preferred. Vinyl chloride copolymer (A
) The degree of polymerization is not particularly limited, but is 400 to 1300.
Those are preferably used.

The vinyl chloride yarn copolymer (B) (CB), the vinyl chloride yarn copolymer used in the present invention, has a VOMR of 9flO to 9!19.
It is a copolymer obtained by copolymerizing 5% by weight of diacrylphthalate (hereinafter referred to as DAP) and 1.0 to 0.05% gold. If the proportion of DAP in the copolymer (B) exceeds 1.0% by weight, the bath melt viscosity will become too high and processability will deteriorate;
If it is less than that, the erasing effect of the molded product will be insufficient.

The vinyl chloride dilute copolymer (B) can be produced by any known vinyl chloride polymerization method, similar to the above-mentioned vinyl chloride thread copolymer (A). Those having a submergence of 400 to 1300 can be preferably used.

Vinyl chloride resin composition: The vinyl chloride resin composition of the present invention contains 50 to 90 weight f of the vinyl chloride copolymer (A).
t% and vinyl chloride copolymer (B) in an amount of 50 to 10 M. The ratio of copolymer (A) in the composition is less than 50% by weight (copolymer CB) is 5
When the ratio of copolymer (A) exceeds 0% by weight), the disadvantages of copolymer (B), such as molded product surface heterogeneity (rough skin phenomenon) and poor processability, become noticeable. If the amount is exceeded, the degree of improvement in the matting effect and thermal stability by the copolymer (B) will be insufficient.

The vinyl chloride thread resin composition of the present invention, like ordinary vinyl chloride, can be used in combination with conventional plasticizers and stabilizers, as well as various fillers, to achieve excellent properties in the fields of hard, semi-hard, and soft. A vinyl chloride molded product with a matte effect can be obtained.

Examples of plasticizers that can be used in the vinyl chloride resin composition of the present invention include 7-tal sulfur plasticizers such as dioctyl phthalate (DOP), diisodecyl phthalate (DiDP), dihexyl phthalate (DHP), and dibutyl phthalate (DBP). The fatty acid plasticizer dioctylazibe) (DOA) is cited as the most popular.
) Diisodecyl adipate (DiDA), other polyester plasticizers, trinolitic acid plasticizers, epoxy plasticizers, etc. may also be used.

These plasticizers can be used alone or as a mixture, and the amount thereof is less than 150 M parts, preferably 100 parts by weight or less, based on 100 parts by weight of the vinyl chloride thread resin composition of the present invention.

Stabilizers that can be used in the vinyl chloride resin composition of the present invention include metal soaps such as lead stearate, cadmium stearate, barium laurate, calcium stearate, and zinc stearate, and organotin stabilizers such as diptyltin maleate. Typical examples include lead compounds such as tribasic lead sulfate, and the amount added is generally 5 parts or less per 100 parts of the compound. Other additives normally used in vinyl chloride resins, such as fillers, pigments, and various antioxidants, can be added as appropriate.

The vinyl chloride resin composition and these compounds may be mixed by the mixing method normally used for blending vinyl chloride resins, for example, using a pump blender, Henschel mixer, tumbler, etc. . The mixture may be subjected to molding as it is as a powdery compound, or may be subjected to molding as a pelletized land by passing it through a pelletizer.

The present invention will be specifically explained with reference to Examples.

In addition, the physical property evaluation methods used in the examples are collectively shown below.

Glossiness: The glossiness of the roll-attached surface (high-speed roll@) of a roll-formed sheet was measured according to JI8 5400K (general paint test method).

Workability: Observe the state of the bank after kneading it with a roll at 180℃ for 10 minutes. Those that are well melted are ○, those that are poorly melted and cloudy with air bubbles are X, and those that are in between these. is indicated as △.

Surface homogeneity: Roll-formed sheets with a homogeneous satin-like matte surface are ○, those with wavy mottling, unevenness, or many particles that do not gel are 1, and all those in between are △. I blurted out.

10- The color tone of the sheet molded with two thermally stable rolls was observed, and those with almost no coloring were marked as ○, and those with significant coloring were marked as ×.

Average degree of polymerization: Measured using the tetrahydrofuran soluble portion of the vinyl chloride copolymer according to J Engineering 5 K6721 (vinyl chloride resin test method).

Examples 1-3. Comparative Examples 1 to 3 A vinyl chloride copolymer (A) was subjected to ethylene to obtain a copolymer (1) having an average degree of polymerization of 700.

As the vinyl chloride copolymer (B), DAPl, Q weight % and VC! A monomer mixture containing MR of 90.0% by weight was polymerized in the same manner as above to obtain a copolymer (2) with an average degree of polymerization of 710.

Each resin composition obtained by mixing the above copolymer (1) and copolymer (2) at the predetermined ratio shown in Table 1 *100
2 parts by weight of a tin-based heat stabilizer were added to the mixture, and using a Henschel mixer, the temperature of the pot was controlled at 130°C, and the mixture was stirred and mixed for 25 minutes to obtain a whole paratha-like compound. This compound was mixed using an 8-inch diameter mixing roll for 18 minutes.
The mixture was kneaded at 0° C. for 10 minutes and formed into a sheet with a thickness of 0.3111 mm. All processability and physical properties of Sealy are shown in Table 1.

Examples 4 to B, Comparative Examples 4 and 5 As the vinyl chloride copolymer (A), PEGA having 14 polymerized units of ethylene glycol and VO
A monomer mixture consisting of MR99° and 0% by weight was heated to 57°C.
Copolymer (3) with an average degree of polymerization of 1030 by suspension polymerization with
I got it. As the vinyl chloride yarn copolymer (B), as shown in Table 1, DAPα05 to 1.2% by weight and 70MR9
A mixture of various monomers consisting of 9.95 to 98.8% by weight f! : Suspension polymerization was carried out at 5'i'°C to obtain copolymers (4 to 9) with an average degree of polymerization of 1020.

The above copolymer +31501'1. each resin composition consisting of 1 m 50 ffiit % of any one of the above copolymers (4 to 9), 40 parts by weight of plasticizer (DOP) and 3P Ba-Zn thermal stabilizer per 1 oo part by weight of WJ.
Add HRi and bring the maximum temperature to 1 using a Henschel mixer.
A compound was obtained by mixing for 20 minutes at a controlled temperature of 10°C.

These compounds were kneaded for 10 minutes at 180°C using a mixing roll with a diameter of 8 inches to give a thickness Q of 3 m.
'y-).

Furthermore, for comparison, a plasticizer and a stabilizer were added to the above copolymer (3) in the same manner as above, mixed and kneaded to a thickness of 0.3
1111 sheets were obtained.

These evaluation results are shown in Table 1.

Examples 9 and 10. Comparative Example 6 As the vinyl chloride copolymer (A), PIGAI with 14 polymerized units of ethylene glycol, Q weight % and 70M
A monomer mixture consisting of R99.0% by weight was suspension polymerized at 52°C to obtain a copolymer (10) with an average degree of polymerization of 1310.
I got it. As the vinyl chloride copolymer (B), D A
A monomer mixture consisting of 1.0% by weight of P and 99.0% by weight of 70MR was similarly polymerized to obtain a copolymer (11) with an average degree of polymerization of 1320.

13- Add 3 parts by weight of a Ba-Zn heat stabilizer and a plasticizer (DOP) to 10 parts of a resin composition consisting of 50% by weight each of the copolymers (10) and (]l), and mix using a Henschel mixer. Mix for 20 minutes at a maximum temperature of 110℃ or less, and the plasticizer mixture lids are 50, 100, and 15, respectively.
A compound containing 0 parts by weight was obtained.

The above compound was kneaded at 180° C. for 10 minutes using a mixing roll with a diameter of 18 inches, and then formed into a sheet having a thickness of 0.3B.

These evaluation results are shown in Table 1.

Examples 11-14. Comparative Example 7 As the vinyl chloride copolymer (A), as shown in Table 1, the number of polymerized units of ethylene glycol was 14 OPEGA 0.
05-4.0% by weight and 70MR99,95-96, OB
Various monomer mixtures consisting of
16) was obtained. DA as vinyl chloride copolymer (B)
A monomer mixture consisting of Pl, Q weight % and VOMRgg, 0 weight % was polymerized in the same manner as 14- to obtain a vinyl chloride copolymer (17) having an average degree of polymerization of 1020. Ba-Zn stabilizer 3 was added to 100 parts by weight of each resin composition consisting of 50% by weight of each of the copolymers (12 to 16) and 50M of the copolymer (17).
．． 0 parts by weight and 40 parts by weight of a plasticizer (DOP) were added, kneaded in the same manner as in Examples 4 to 8, and formed into a sheet with a thickness of 0.3111 mm. These evaluation results are shown in Table 1.

Comparative Examples 8 to 10 The PEGA content used in Examples 11 to 13 was 0.
05, 0.50, and 2.0% by weight of the vinyl chloride copolymers (12 to 14) were blended with a stabilizer and a plasticizer in the same manner as in Bone Example 11, and then mixed and molded. These evaluation results are shown in Table 1.

Examples 15-19. Comparative Example 11.12 As the vinyl chloride copolymer (A), PKGMl with 14 polymerized units of ethylene glycol, Q weight % and vaMR
A monomer mixture consisting of
)'r got it. The vinyl chloride yarn copolymers (4-8) used in Examples 4-8 were blended with this copolymer (1 day) as shown in Table 2, and stabilizers and plasticizers were added in the same manner as in Example 4. were mixed and kneaded to form a sheet with a thickness of 0.3 fins.

Separately for comparison, the above vinyl chloride copolymer (1B) 3
0% by weight of a copolymer mixture consisting of 70% by weight of vinyl chloride copolymer (B), and 2 loaM parts of a bone stabilizer.
．． A composition in which 0 double parts were blended (Comparative Example 11), and a composition in which 2.0 parts by weight of an sn-based stabilizer was blended with 100 parts by weight of vinyl chloride copolymer (1B) (Comparative Example 1'2). The mixture was kneaded in the same manner as in Example 1 and formed into a sheet with a thickness of 0.3 mm.

These results are shown in the second coat.

Examples 20-23. Comparative Example 13.14 Examples 11 to 14 were repeated, except that PEGM having 14 polymerized units of ethylene glycol was used as the synthetic component of the vinyl chloride copolymer (A). . For comparison, a vinyl chloride copolymer (B) containing no Th (Comparative Example 13) and a vinyl chloride homopolymer (Comparative Example 14) K: were also evaluated.

These evaluation results are shown in Table 2.

17-

Claims (1)

[Claims] 1) Vinyl chloride yarn consisting of 97.0 to 99.95 weight units of vinyl chloride and 3.0 to 0.05 weight units of polyethylene glycol diacrylate or polyethylene glycol dimethacrylate having 4 to 50 polymerized units of ethylene glycol. Copolymer (A) 50 to 90 coulomer, and vinyl chloride thread copolymer (B) consisting of 99.0 to 99.953 iit of vinyl chloride and 1.0 to 0.05% by weight of diallyl phthalate. A vinyl chloride resin composition comprising 10 coulometric units.