JPS60195147A - Composition for semirigid vinyl chloride resin moldings - Google Patents

Abstract

PURPOSE:A composition that is obtained by adding a specific polyester plasticizer and other stable copolymer resin at a specific ratio, thus being suitable for forming marking films, because it has an appropriate level of toughness and gives moldings with high flexibility. CONSTITUTION:The objective composition is obtained by combining (A) 100pts. wt. of a vinyl chloride resin containing 0-20wt% of copolymer components, with (B) 1-20pts.wt. of a liquid polyester plasticizer of more than 1,500 number-average molecular weight such as obtained from 4-15C dibasic acid and 2-20C dihydric alcohol, (C) 0-10pts.wt. of other plasticizers for vinyl chloride resins and (D) 45-350wt%, based on the total of B and C, of a plasticizer of a copolymer ethylene with carbonyl in the main chain/vinyl ester of saturated carboxylic acid such as vinyl acetate/carbon monoxide so that the yield stress is adjusted to 1-6kg/mm.<2>. EFFECT:The composition gives moldings with high adhesion to a pressure-sensitive adhesive and good printability.

Description

Detailed Description of the Invention The present invention is suitable for molding semi-rigid vinyl chloride resin molded products such as films, sheets, overlay films, and laminating films, and has excellent properties particularly as a marking film molding composition. This invention relates to a semi-rigid vinyl chloride resin molding composition.

For more details, yield stress 1~6X? /Ig", flexibility with appropriate stiffness, adhesive strength retention of the pressure-sensitive adhesive when a pressure-sensitive adhesive layer is provided on the film of the composition, printing on the film. It is an improved film that has excellent properties such as adhesion between printing ink and film when applied, weather resistance, suitability for adhesion to curved surfaces when used as a marking film, and ultraviolet absorber retention. The present invention relates to a semi-rigid vinyl chloride resin molding composition.

In particular, the present invention provides (A) 100 parts by weight of a vinyl chloride resin containing a copolymerized component of 0 to about 20% by weight, ω) a liquid having a number average molecular weight (Mn) of about 1.500 or more; about 1 to about 20 parts by weight of a polyester plasticizer and 0 to about 10 parts by weight of another plasticizer for vinyl chloride resin, and C) ethylene/vinyl ester of saturated carboxylic acid/-
an ethylene/vinyl ester resin having -C- bonds in the main chain consisting of a carbon oxide copolymer resin in an amount of about 45 to about 350% by weight based on the total amount of the above ω) plasticizer; Contains a material with a yield stress of 1 to 6 kg/rt.
The present invention relates to a semi-rigid vinyl chloride resin molding composition characterized in that it is RRA 2.

Conventionally, vinyl chloride resins have been known to have different degrees of plasticization, ranging from soft vinyl chloride resins plasticized with liquid plasticizers to hard vinyl chloride resins that have not been plasticized. Depending on the situation, resins exhibit a wide range of physical properties, ranging from rubber-like elastic bodies to rigid bodies, and are put to practical use in a variety of applications. Furthermore, it is generally known that various acrylic resins are blended with vinyl chloride resin for the main purpose of improving moldability. Efforts have been made to provide compositions.

In soft to semi-rigid vinyl chloride resin molding compositions, the amount of plasticizer blended is usually relatively large, and problems related to plasticizer bleed-out or plasticizer bleed-out may occur. Since the problem of deterioration of the physical properties of vinyl chloride resin is involved, proposals have been made to overcome this problem. However, the reality is that a satisfactory composition cannot be provided.

The present inventors have worked hard to develop a semi-rigid vinyl chloride resin molding composition that has excellent properties as a semi-rigid vinyl chloride resin molded article, particularly as a marking film molding composition.

As a result, the number average molecular weight (M
n) A liquid polyester plasticizer that satisfies the conditions of about 1 to
About 20 parts by weight, and the above C) ethylene/vinyl ester resin having 1 -c-JLa- in its main chain consisting of ethylene/vinyl ester of saturated carboxylic acid/carbon oxide copolymer resin; (J3) about 45 to about 3 based on total amount of plasticizer
By satisfying the bonding parameters of 50% by weight and 8% yield stress and a yield stress of 1 to 6 kli'/rran2, a flexible, pressure-sensitive adhesive layer with appropriate stiffness can be created. The adhesive strength of the pressure-sensitive adhesive when applied on a film of the composition, the adhesion between the printing ink and the film when printed on the film, the weather resistance, and the properties of the pressure-sensitive adhesive when used as a marking film. In terms of suitability for adhering to curved surfaces and UV absorber retention,
It has been discovered that it is possible to provide a semi-rigid vinyl chloride resin molding composition that has both of these excellent properties, and in particular has excellent properties desired in a marking film molding composition.

For example, motorcycles, four-wheelers and other vehicles, land and sea containers, yachts, ports and other vessels, ships and containers, furniture, door boards, window frames, pillars, etc. Striped stickers for decoration or display of building materials; advertising stickers used to display advertising characters, figures, patterns, etc. on signboards and advertising boards: traffic signs, road signs, information boards, danger signs, etc. Various display stickers such as prevention signs and product marks;
Marking films are used in a wide range of fields such as:

Such a marking film is used in such a manner that, for example, a suitable pressure-sensitive adhesive layer is provided on one side and a suitable release paper is attached on the adhesive layer, and the release paper is peeled off before use. It is used in such a manner that it is attached to a desired part of a desired base material. However, in conventional marking films, there has been a problem in that the plasticizer in the film predominates in the adhesive layer, reducing its adhesive strength over time and deteriorating its adhesive strength to the substrate. Furthermore, the plasticizer in the film bleeds out to the surface of the marking film opposite to the adhesive layer, promoting the adhesion of dust in the air and easily contaminating the surface of the marking film, resulting in poor weather resistance. There is also a problem with this. Furthermore, when printing is applied to the surface of a marking film, conventional marking films have problems in that the adhesion between the printing ink and the film is insufficient and the film easily peels off, and furthermore, it is unsatisfactory in terms of suitability for adhering to curved surfaces. Met. Furthermore, since marking films are often used on a monthly basis, it is common to include UV absorbers in them, but in conventional marking films, the UV absorbers tend to evaporate due to heat during film molding. However, such films also have a problem of poor ultraviolet absorber retention after molding.

In soft to semi-rigid vinyl chloride resin molding compositions, the amount of plasticizer blended is usually relatively large, and in marking films, it is particularly important to avoid plasticizer bleed-out or bleed-out as described above. There is an issue of physical property deterioration involved.

Furthermore, in order to satisfy the adhesion or adhesion performance of the marking film to a desired part of a desired base material, such as a curved surface,
It is necessary to impart flexibility to the film with appropriate stiffness. However, it contains the amount of plasticizer required for a soft to semi-rigid vinyl chloride resin film, overcomes the problems directly or indirectly related to the bleed-out of the plasticizer, and has an appropriate yield stress. It has been extremely difficult to provide a vinyl chloride resin molding composition that has both flexibility and appropriate stiffness.

According to the research of the present inventors, it has been found that up to about 5 parts by weight of other plasticizers for vinyl chloride resins may be used in combination with 100 parts by weight of the vinyl chloride resin (5). About 1 to about 20 parts by weight of a liquid polyester plasticizer that satisfies the number average molecular weight (Mn) condition in the range, and the above (O) ethylene/saturated carboxylic acid vinyl chloride resin, above (B)
meeting bonding parameters of from about 45 to about 350 wt., based on total amount of plasticizer, and having a yield stress of 1 to 6 kg/
The above-mentioned difficulties were overcome by satisfying the bonding requirement of 'ran', and as will be shown experimentally later by giving examples and many comparative examples, semi-rigid vinyl chloride has excellent improved properties. It has now been discovered that resin molding compositions, in particular marking film molding resin compositions and molded articles can be provided.

Accordingly, an object of the present invention is to provide a semi-rigid vinyl chloride resin molding composition, particularly a marking film molding composition, which has improved properties.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

When molding a film using the semi-rigid polyvinyl chloride resin molding composition of the present invention, there are no particular restrictions on the molding method, and there are no special restrictions on the molding method, and there is no particular restriction on the molding method. (THF), methyl ethyl ketone (MEK), etc. to obtain a film by casting and drying.Furthermore, the solid component of the composition is dispersed in a sol state, which is then cast and melted by heat. Examples include forming methods such as sol casting to obtain a film.

In general, films produced by the casting method are particularly preferable in that they have less distortion than the thermal processing method.

There are no particular restrictions on the vinyl tetrachloride resin used in the semi-rigid vinyl chloride resin molding composition of the present invention, and vinyl chloride resins conventionally used for molding can be appropriately selected and utilized. For example, the degree of polymerization is about 600 to about 3000
Examples include vinyl chloride resins having a polymerization degree of preferably about 700 to about 2,000, more preferably about 800 to about 1,800, particularly preferably about 1,200 to about 1,600. Furthermore, the vinyl tetrachloride resin can also be a resin for vinyl chloride paste.

The above-mentioned vinyl tetrachloride resin is a copolymer containing, in addition to the vinyl chloride homopolymer, up to about 20% by weight, preferably about 10% by weight, particularly preferably up to about 6% by weight of a copolymer component. I can do it.

Examples of such copolymer components include vinyl monomers, olefinic monomers such as ethylene, propylene, butylene, isobutylene, etc., butadiene,
Diene and vinyl acetylene derivatives such as chlorbutadiene, pentadiene, etc.

For example, vinyl halide monomers such as vinyl fluoride, vinylidene chloride, vinyl bromide, etc. For example, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, propyl methacrylate, ethylene glycol dimethacrylate, etc. (meth)
Acrylic acid ester monomer. For example, vinyl ester monomers such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate, and the like. For example, vinyl ether monomers such as methyl vinyl ether, propyl vinyl ether, butyl vinyl ether, phenyl vinyl ether, allyl vinyl ether, and the like. Examples include styrene-derived C1O copolymers such as styrene, methylstyrene, dimethylstyrene, vinylstyrene, chlorstyrene, vinylphenol, and the like.

The vinyl chloride resin (4) described above can be produced by a method known per se, such as a suspension polymerization method or an emulsion polymerization method, or can be obtained on the market. For example, Nika Vinyl 5G-700, 5G-800, 5G-1100, 5G-
1300, 5G-1400 [vinyl chloride resin, Ryoichi Co., Ltd. product or Nippon Carbide Industries Co., Ltd. product], Zeon 121, Zeon 131, Zeon 25 Mizeon 135J
(vinyl chloride resin, Nippon Zeon Co., Ltd. product), Vinyryoku 51 MF, Vinyryoku P-440, Vinyryoku P-400 [vinyl chloride resin, Mitsubishi Monsanto Co., Ltd. product], Sumilit PX [vinyl chloride resin, Sumitomo Chemical Co., Ltd. Commercially available vinyl chloride resins such as [Product] can be exemplified.

C used in the semi-rigid vinyl chloride resin molding composition of the present invention
B) The plasticizer is (5) vinyl chloride resin 100 as described above.
The number average molecular weight (Mn) is approximately 1.50 based on the weight part.
0 or more, preferably about 1,500 to about 6. OOOl preferably about 1,500 to about 4.0 (10, more preferably about 2,000 to about 4.00) OOO polyester plasticizer about 1 to about 20 parts by weight, preferably about 1 to about 15 Parts by weight, more preferably about 2 to about 10 parts by weight and O to about 1 part by weight
0 parts by weight of other plasticizers for vinyl chloride resins.

Examples of such liquid polyester plasticizers include 1 to 3 types of dibasic acids selected from C4 to CI5 dibasic acids such as maleic acid, adipic acid, phthalic acid, azelaic acid, and sebacic acid, and ethylene, for example. glycol, 1,2
-propylene glycol, ], ] 3-butylene glycol 1,3-butanediol, 1,4-butanediol,
Neopentyl glycol, dipropyl glycol, 1.
6-hexanediol, 2,2,4-trimethyl 1,3
- 1 selected from C2 to C20 dihydric alcohols such as hentanediol, 1,5-bentanediol, etc.
Examples include liquid polyester plasticizers obtained by reacting five types of polyester plasticizers with a chain stopper appropriately selected from acetic acid, coconut oil fatty acid, n-octyl alcohol, and n-decyl alcohol. Among these, one or two selected from adipic acid, phthalic acid, and maleic acid, and one or two selected from propylene glycol, dipropyl glycol, hexanediol, and butanediol.
A preferred example is a liquid polyester plasticizer derived from these three types.

The liquid state of the liquid polyester plasticizer of the present invention means a viscous liquid with a viscosity at 25°C of 500,000 voise or less as measured by a BH type rotational viscometer, and the number average molecular weight of the polyester plasticizer (
Mn) is GPC (Gel.

Permeation (: chromatograph
y) method and converted.

Such polyester plasticizers are commercially available and can be used in the present invention.

Examples of such commercially available polyester plasticizers include P
N-150, PN-260, PN-446 (polyester plasticizer, product of Adeka Argus Chemical Co., Ltd.), NS
-3700 (polyester plasticizer, Dainichiseika Chemical Co., Ltd. product), P-204N, P-29 (polyester plasticizer, Dainippon Ink & Chemicals Co., Ltd. product), G-2
5, G-40 (polyester plasticizer, Rohm & Haas product), 5P-17'l, DIDA, 5P-501,
5P-1158 (polyester plasticizer, Sanken Chemical Co., Ltd. 1 ρ product), Kodaflex NP 10 (polyester plasticizer, Eastman Chemical Co., Ltd.)
Products), Flexol R-2H
(Polyester plasticizer, [n1on Carbide
Corp.

Henke 1 product), Edenol 1200 (polyester plasticizer, Henke 1 product), RheopleX 1
00, Rheoplex 110, Rheoplex 2
20 (Polyester plasticizer, Ciba-Geigy
Company products) Examples manufactured by the company can be shown. Such polyester plasticizers can be used not only alone, but also in combination of two or more kinds.

In the composition of the present invention, (4) vinyl chloride ≠
Other plasticizers for vinyl chloride resins may be used in small amounts, up to about 10 parts by weight, preferably about 5 parts by weight, based on 100 parts by weight of the resin. Examples of such other plasticizers for vinyl chloride resins include C2-C311 mono- or polybasic esters of C8-C0 mono- or polyhydric alcohols of luponic acid and oxiranes with an oxygen content of 2
~9M molecular weight approx. OOO or less, for example about 1
0 to about 4000 epoxy compounds may be mentioned.

Such other plasticizers for vinyl chloride resins can be exemplified.

For example, dimethyl phthalate, diethyl phthalate,
Dibutyl phthalate, di(2-ethylhexyl) phthalate, di-n-octyl phthalate, higher alcohol phthalate, diyneoctyl phthalate, diisobutyl phthalate, diethyl phthalate, diindecyl 7-vinyl phthalate, citridecyl phthalate, diundecyl C4 to C0 monovalent phthalic acids such as phthalate, di(heptylnonylundecyl) phthalate, benzyl phthalate, butylbenzyl phthalate, dinonyl phthalate, normal alkyl phthalate, di-n/isoalkyl phthalate, etc. or polyhydric alcohol ester; for example, dimethyl inphthalate)
C1 to Csa monohydric or polyhydric alcohol ester of isophthalic acid such as -(2-ethylhexyl)-isophthalate, diyneoctyl isophthalate, polyalkylene glycol isophthalate, etc.;
-ethylhexyl)tetrahydrophthalate, di-n-
C0-("
++ monovalent it-<'s alcohol esters: for example, di-n-butyl adipate, di(2-ethylhexyl) adipate, diisodecyl adipate, benzyl octyl adipate, di(butoxy ethoxyethyl) adipate, etc. monohydric or polyhydric alcohol esters of c+-css of adipic acid such as; Monohydric or polyhydric alcohol esters of C3I+; for example, di-n-butyl sebacate, di(2-ethylhexyl) sebacate, etc. monohydric or polyhydric alcohol esters of C3 to C0; e.g. , di-n-butyl
C8-CSS monohydric or polyhydric alcohol esters of chimaleic acid such as maleate, dimethyl maleate, diethyl maleate; Tatoeha, di-n-butyl fumarate, di(2-ethylhexyl) fumarate, etc. C1 to CSa monohydric or polyhydric alcohol esters of fumaric acid such as l:, tb,) C1 to C35 of trimellitic acid such as di(2-ethylhexyl) trimellitate, trilooctyl trimellitate, triisodecyl trimellitate, etc. monohydric or polyhydric alcohol esters; for example, monohydric or polyhydric alcohol esters of CI"C35 of citric acid, such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, etc.; for example, monomethyl itaconate; C8-CSa monohydric or polyhydric alcohol esters of itaconic acid such as , monobutyl itaconate, dimethyl itaconate, etc.; oleic acids such as butyl oleate, tetrahydronorinoleate, glyceryl monooleate, etc. C1 to C35 No. 1 (d
mot, <' is a polyhydric alcohol ester; for example, methyl acetyl lysate, butylacetyl lysylt,
Monohydric or polyhydric alcohol ester of CI"C311 of ricinoleic acid such as glyceryl monolysyllate; stearic acid such as Tatoel ld', n-butyl stearate, glyceryl monostearate, diethylene glycol distearate, etc. Monohydric or polyhydric alcohol esters of C, ~CS++; Others diethylene glycol monolaurate, benzenesulfone butyramide, trimethyl phosphate, tryptoxyethyl phosphate, tetra-2-ethylhexylpyromellitate, diethylene glycol dibenzoate, glycerol - Monoacetate, chlorinated paraffin, oxirane Epoxy derivatives with an oxygen content of 2-9 molecules Ji of 1000 or less.

The semi-rigid vinyl chloride resin molding composition of the present invention contains (C) ethylene/vinyl ester of saturated carboxylic acid/-oxidation together with the above-mentioned (4) vinyl chloride resin and ω) liquid polyester plasticizer. The ethylene/vinyl ester resin having a -bond in the main chain consisting of a carbon-based copolymer resin is added to an amount of about 45 to
It contains about 350% by weight, preferably about 50 to about 300% by weight.

The ethylene/third monomer/-carbon oxide copolymer resin that can include the copolymer resin of (O) used in the composition of the present invention and its judgment are known (for example, Japanese Patent Publication No.
No. 50063; JP-A No. 48-26228), which are commercially available (for example, “El Paloy” product of DuPont, USA) and which satisfy the requirements specified in the above (O) in the present invention. You can choose and use it.

The above-mentioned Japanese Patent Publication No. 55-50063 describes a wide range of copolymer resins that can include the above-mentioned copolymer resin (C) used in the present invention, and describes combinations with polar polymers such as polyvinyl chloride. It has been described that it is useful for improving the properties of

However, this well-known publication also describes the bonding parameters of the special chill-based plasticizer and the specific copolymer resin (C) in the present invention, as well as the existence of technical problems in the marking film and the problems. There is no description or suggestion whatsoever regarding the superior effects of the composition of the present invention that can be achieved by overcoming the above.

In the composition of the present invention, as the copolymer resin (C), ~C- Ethylene/vinyl ester resins with bonds are selectively used.

Examples of vinyl esters of saturated carboxylic acids include vinyl esters of C1 to C1g saturated carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate. Among these, C2
Vinyl esters of ~C4 saturated carboxylic acids such as vinyl acetate and vinyl propionate are more preferred. The copolymer resin has a -C- bond in the main chain, and this bond has an infrared absorption spectrum (
It can be detected as absorption near 1715cn-' in IR). These vinyl esters usually exhibit a bond. The composition range of ethylene, vinyl ester of saturated carboxylic acid, and -carbon oxide in the zero copolymer resin to be used can be selected from a wide range + as appropriate.
) 20-94% by weight of ethylene, (b) 5-50% by weight of vinyl esters of saturated carboxylic acids, and (C) 1% by weight of carbon oxide.
~30% by weight; preferably (a) 40-82% by weight;
(b) 15-40% by weight and (C) 3-20% by weight; preferably (a) 55-75% by weight, (b) 20-20% by weight
A composition range of 30% by weight and (C) from 5 to 15% by weight may be exemplified.

As explained in detail above, the semi-rigid vinyl chloride resin molding composition of the present invention contains (g) 0 to about 20% by weight, preferably 0 to 10% by weight, more preferably 0 to about 6% by weight. CB) has a number average molecular weight (Mn) of about 1,500 or more, preferably about 1,500 to about 6,000, more preferably about 1 ,500 to about 4,000, more preferably about 2,0
00 to about 4,000 liquid polyester plasticizer to about 1
~20 parts by weight, preferably about 1 to about 15 parts by weight, preferably about 2 to about 10 parts by weight, and O to ~10 parts by weight of other vinyl chloride resin plasticizers, preferably 0 to about 5 parts by weight and C) ethylene/vinyl ester resin having 1 K C1g in the main chain consisting of ethylene/vinyl ester of saturated carboxylic acid/carbon oxide copolymer resin, based on the total amount of plasticizer in 03) above. Approximately 45 to 350
% by weight, preferably from about 50 to about 300% by weight, and has a yield stress of 1 to 6 kc9/m.
m”, preferably 1 to 5, more preferably 1.2 to 4
．． 5 units/rtas2.

By satisfying the above-mentioned bonding requirements, the composition of the present invention has flexibility with appropriate stiffness, and adhesive strength retention of the adhesive when a pressure-sensitive adhesive layer is provided on the composition film. , adhesion between the printing ink and the film when printing is performed on the film, weather resistance under outdoor usage conditions, suitability for adhering to curved surfaces when used as a marking film, and ultraviolet absorber retention, etc. It has all of these excellent properties.

It is presumed that the above-mentioned components (G), Φ), and (C) mutually influence each other for the composition of the present invention to have the above-mentioned excellent properties. Although it is difficult to unambiguously describe the effect, as will be shown experimentally with many comparative examples and examples later, if the binding requirements specified in the present invention are deviated from, the above-mentioned effects in the composition of the present invention In practice, it is extremely difficult to achieve a combination of excellent properties.

When the tetracarboxylic vinyl resin contains a copolymer component, the amount of the copolymer component is up to about 20% by weight, preferably up to about 10 parts by weight, and more preferably up to about 6 parts by weight. If the copolymerization component is in an excessive amount exceeding the above amount, it tends to cause disadvantages such as a decrease in thermal stability and a colored film, so it should be used in an amount of about 10% by weight or less. It is better.

(4) The degree of polymerization of the vinyl chloride resin can be selected as appropriate, but as mentioned above, the degree of polymerization is about 600 to about 3000, preferably about 700 to about 2000, more preferably about 80.
0 to about 1800, particularly preferably about 800 to about 160
For example, a value of about 0 indicates good solubility in the solvent used when using the solution casting method, excellent viscosity properties (perspiration properties), and stability against heat when using the calendering method, for example. and good meltability,
It is convenient to use a vinyl chloride resin having a polymerization degree of (4) as exemplified above, since very favorable results can be obtained.

The number average molecular weight (Mn) of the polyester plasticizer (B)
) is about 1.500 or more, preferably about 1.500 to about 6
,000, preferably about 1,500 to about 4,000
furthermore, from about 4000 to about 4,000, particularly from about 2,000 to about 3.200.

If the above amount is too low, less than 1,500, the tendency of plasticizer bleed out will increase unfavorably under the combination requirements of (4) and other requirements of C), and the adhesive strength, weather resistance, ultraviolet absorption This causes a non-negligible deterioration in terms of agent retention, etc. On the other hand, when a solid polyester plasticizer is used in place of a liquid polyester plasticizer, the elongation rate of the film decreases and the film becomes undesirably brittle. Therefore, as the liquid polyester plasticizer (ω), a polyester plasticizer that satisfies the above number average molecular i (Mn) condition is selected and used.

Furthermore, the amount of liquid polyester threaded plasticizer used is (
4) About 1 to about 20 parts by weight of vinyl chloride resin
Parts by weight, preferably about 1 to about 15 parts by weight, more preferably about 2 to about 10 parts by weight, but if the amount of the liquid polyester plasticizer (B) used is too small and deviates from the above range, , under the requirements of combination with other requirements of
In addition, if the amount exceeds the above range and is excessive, the adhesive strength will be reduced, and the adhesion between the printing ink and the film will be reduced.
This also causes deterioration in weather resistance, ultraviolet absorber retention, etc. Therefore, the amount should be selected appropriately within the above range.

Furthermore, the amount of other vinyl chloride resin plasticizers that may be used in combination with the above liquid polyester plasticizer is (4) up to about 10 parts by weight, preferably up to about 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. be. If the amount of other plasticizers exceeds about 10 parts by weight and is too excessive, bleed-out will increase, adhesive strength will decrease, and the adhesion between printing ink and film, weather resistance, and ultraviolet absorption will deteriorate. This is undesirable because it causes deterioration in agent retention.

and about 45 to about 350% by weight based on the total amount of plasticizer (the amount of O ethylene/vinyl ester resin is above);
It is preferably about 50 to about 300% by weight.

If the amount of the component (0) used is too small and deviates from the above range, the appropriate flexibility of the film, combined with other requirements, will be impaired, the film will be inferior, and wrinkles will occur. 1. When used as a marking film, the suitability for adhesion to curved surfaces tends to decrease, and if it exceeds the above range, the film becomes soft and stretches, making it difficult to work when used as a marking film. In addition, printing ink adhesion and weather resistance tend to deteriorate.

The semi-rigid vinyl chloride resin molding composition of the present invention contains K(A), CB) and C) under conditions that satisfy the above bonding requirements, and has a yield stress of 1 to 6'Q/ran.
”, preferably 1 to 5 to 9/2, more preferably 1.
2 to 4.5 kg/rtrrB”.

Compositions with a yield stress of zero or close to zero, such as ordinary soft vinyl chloride resin compositions containing a relatively large amount of liquid plasticizer, are flexible enough to have the appropriate stiffness required in the present invention. Therefore, the yield stress is selected to be within the above range. If the yield stress deviates from the above range and is too low, the film will stretch when attached to the intended adherend, making it difficult to attach it to the specified location and size, resulting in poor appearance. . On the other hand, if the adhesive is too high outside the above range, if the adherend has a curved surface, it will not conform to the curved surface and will be wrinkled, making it impossible to apply the adhesive uniformly.

Therefore, in the present invention, the yield stress should be appropriately selected so as to fall within the above yield stress range.

Furthermore, the composition of the present invention has [F]) number average molecular weight (Mn
) is about 1,500 to about 50,000 and is solid at 23° C., in an amount of up to about 20% by weight based on the vinyl chloride resin (5). This is preferable because it further improves adhesive strength retention and weather resistance.

Such low molecular weight acrylic or methacrylic resins have a number average molecular weight (Mll) of about 1,500 to
about 50,000, preferably about 2,000 to about 40,000
00, YO) Preferably about 2,500 to about 30, OOO
Low molecular weight acrylic resins that are solid at 23° C. are available. Up to about 20 fi, preferably about 5 to about 15 weight, based on (g) vinyl chloride, preferably about 7
It is best utilized in an amount of ~12 parts by weight.

As the (2) solid low molecular weight acrylic or methacrylic resin, any low molecular weight acrylic resin that satisfies the above number average molecular weight (Mn) conditions and is solid at 23° C. can be used. Preferred acrylic resins include C1-CI8 alkyl esters of acrylic acid and O1 of methacrylic acid.
- Homopolymers and copolymers comprising at least one acrylic or methacrylic alkyl ester selected from the group consisting of Cl alkyl esters, and which may further contain other copolymerizable components, Examples include low molecular weight acrylic resins that satisfy the number average molecular weight (Mn) conditions and are solid at 23°C.

Specific examples of the C1-C1δ alkyl ester of acrylic acid and the C1-CI8 alkyl ester of methacrylic acid include, for example, acrylate methyl acrylate ethyl acrylate n, propyl acrylate iso, propyl acrylate n, butyl acrylate iso, butyl acrylate cyclohexyl acrylate 2・Ethylhexyl acrylate stearyl acrylate methoxyethyl acrylate ethoxyethyl acrylate butoxyethyl acrylate methoxypolyethylene glycol acrylate 2 ・hydroxyethyl acrylate 2 ・hydroxypropyl acrylate 2 ・hydroxy 3 ・chloropropylacrylate dimethylamine ethyl acrylate diethylamine ethyl acrylate Glycidyl acrylate 2/Chloroethyl acrylate 2/3 Dipromoprobyl acrylate Triflomphenylacrylate Allyl acrylate Oleyl buacrylate Eboxystearyl acrylate Polyethylene glycol diacrylate Hexane glycol diacrylate Neopentyl glycol diacrylate Dipropylene glycol diacrylate Trimethylol propane Triacrylate Tetramethylolmethane Triacrylate 2
・Methyl 3. Sulfoprobyl acrylamide Calcium diacrylate Magnesium diacrylate Barium diacrylate Zinc diacrylate Aluminum triacrylate Lead diacrylate Sodium acrylate Methacrylate Methyl methacrylate Ethyl methacrylate Provyl methacrylate iso・Provyl methacrylate n・Butyl methacrylate iso・Ptermethacrylate Tertiaryptermethacrylate Cyclohexyl methacrylate Octer methacrylate 2・Ethylhexyl methacrylate Lauryl methacrylate Stearyl methacrylate Methoxyethyl methacrylate Ethoxyethyl methacrylate Butoxyethyl methacrylate Methoxypolyethylene glycol 2・Hydroxyethyl methacrylate 2・Hydroxyglobyl methacrylate 2・Hydroxy・3.Chloroprobyl methacrylate polypropylene glycol heptanomethacrylate dimethylaminoethyl methacrylate diethylamine ethyl methacrylate glycidyl methacrylate tetrahydrofurfuryl methacrylate 2.chloroethyl methacrylate allyl methacrylate oleyl methacrylate eboxystearyl methacrylate ethylene glycol dimethacrylate polyethylene glycol dimethacrylate butylene glycol dimethacrylate Examples include methacrylate hexane glycol dimethacrylate neobentel glycol dimethacrylate polyglobylene glycol dimethacrylate trimethylolpropane trimethacrylate.

The zero solids low molecular weight acrylic resin may further contain other copolymerizable components. The content/tolerance can be appropriately changed and selected within a range such that the zero solid acrylic resin satisfies the number average molecular weight (Mn) condition. For example, the amount may be about 100 parts by weight or less, preferably about 30 parts by weight or less, based on 100 parts by weight of acrylic ester or methacrylic ester.

Such other copolymerizable components (or modified monomers)
Examples include olefinic monomers such as ethylene, propylene, butylene, and isobutylene; dienes and vinyl acetylene derivatives such as butadiene, chlorobutadiene, pentadiene, etc.; such as vinyl acetate, vinyl chloroacetate, vinyl propionate, etc. Vinyl ester monomers such as vinyl laurate; vinylmodyl or vinylidene monomers such as vinyl chloride and vinylidene chloride; vinyl ether monomers such as methyl vinyl ether, flobyl vinyl ether, butyl vinyl ether, phenyl vinyl ether, etc.; Styrene derivatives such as styrene, methylstyrene, dimethylstyrene, and vinylphenol; ethylenically unsaturated monomers having carboxyl groups such as maleic acid, fumaric acid, crotonic acid, acrylic acid, methacrylic acid, and itaconic acid; acrylic acid Examples of copolymerizable components include other acrylic monomers such as chloride, acrylonitrile, acrylamide, and N-tert-butylacrylamide.

The zero component that can be used in the present invention is a low molecular weight acrylic or methacrylic resin that has a number average molecular weight (Mn) of about 1,500 to about 50,000 and is solid at 23°C. Advantageously, the glass transition temperature (Tg) is preferably 30°C or higher, more preferably 35°C or higher.

Here, the glass transition temperature (Tg) is calculated from "Mechanical Properties of Polymers" by L. E. Nielsen, translated by Nobuharu Onogi (1966).
It means the Tg determined by the method described on pages 11 to 35 of Kagaku Dojinsha, published on April 15, 2015, and in the case of copolymers, the Tg determined by the method described on pages 26 to 27 of the same book. It means the calculated and determined Tg.

That is, the Tg of the copolymer was calculated using the following formula.

(However, w, +w2+ . . . -wo=1) In the above formula, Tg is the copolymer glass transition temperature, and is calculated by converting it into an absolute temperature. Tg, , Tg, ... and Tgn
Each monomer component 1, component 2, composing the U copolymer...
For each of ... and component n, it is the glass transition temperature of pure homopolymer 1.2 ... and n, and is calculated in terms of absolute temperature. W, , Wt... and Wn are the weight fractions of the respective components constituting the copolymer in the copolymer.

Tg ('K) of the homopolymer for each monomer component above
) are known and are illustrated in Table A below. In addition, in the table,
The monomer symbols are as follows. Also, using the values shown in Table (A), MMA-BMA-BA (60% by weight
-30% by weight - 10% by weight), the Tg of the resin obtained is 0.

Table A Methyl acrylate MA 273 Ethyl # EA 246 n-Butyl # n-BA 216 t-Butyl # t-BA304 2-Ethylhexyl $ 2EHA 2132-Hydroxyethyl ” ZHEA 273 Octyl da OA
208 Acrylic acid AA 439 Acrylamide AAMD 426 Methyl methacrylate MMA 376 Ethyl 'l
EMA 320 n-bufk # n-BMA 294 2-hydroxyethyl # 2HEMA 328 Methacrylic acid MAA 458 Vinyl acetate vAC306 Table A (continued) Propyl acetate VP r 266 Styrene St 363 Acrylonitrile AN 379 Vinyl chloride VCI 353 Vinylidene chloride VdC1258 Ethylene Et 196 Butadiene Bd 183 Vinyl pasatuccinate v■ 270 The number average molecular weight (
Mn') is about 1,500 to about 50,000, preferably about 2,000 to about 40. It is OnO. If it deviates from the above range and is too small, there is a tendency for the plasticizer in requirement (6) to bleed out under the combination requirements with other requirements (4) and ω), especially as a combination parameter with (6). This results in a significant increase in adhesive force retention, weather resistance, etc., which cannot be ignored. Furthermore, the low molecular weight acrylic resin itself tends to bleed out, and this tendency
In the case of low-molecular-weight acrylic resins that do not meet the requirements for solidity and are liquid at 25°C, problems such as bleed on the film surface and further worsening of adhesion retention and weather resistance occur. However, there are also disadvantages in terms of UV absorber retention. Furthermore, the number average molecule t(Mn>
If it deviates from the above range and becomes excessive, the appropriate flexibility of the film will be impaired, and the advantage of moderate flexibility with appropriate stiffness under the combination of the other requirements of (G) and (B) will be lost. Further, when molding into a film structure by employing a calendaring method, for example, the low molecular weight acrylic resin (6) tends to decompose and discolor. Therefore,
(c) When using the resin, the number average molecular weight (M
Low molecular weight acrylic resins that are solid at 23° C. and within the range 11.

The amount of the low molecular weight acrylic or methacrylic resin used is up to about 20 parts by weight based on (4) vinyl chloride. If the amount of the low molecular weight acrylic resin (D) used is too large, the appropriate flexibility of the film will be impaired in combination with other requirements, and the film will not have adequate flexibility with appropriate stiffness. The profits shown tend to decline. Therefore,
When the low molecular weight acrylic or methacrylic resin (D) is used, the amount used should be appropriately selected to be about 20% or less based on the vinyl chloride resin (5) above.

The semi-rigid vinyl chloride resin molding composition of the present invention can further contain various other additives.

Examples of such other additives include, for example, colorants,
Examples include metal powder, crushed metal foil powder, lubricants, stabilizers, antifogging agents, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, and foaming agents.

Examples of the above colorants include titanium oxide, zinc white, lead white,
Calcium carbonate, gypsum, precipitated silica, carbon black, Ingara, mica, molybdenum red, cadmium yellow,
Inorganic pigments such as yellow lead, titanium yellow, chromium oxide green, and ultramarine; organic pigments such as Permanent Red 4R Hansa Yellow 10G1 Benjishi Yellow GR1 Permanent Carmine FB, Phthalocyanine Blue B, and Phthalocyanine Clean; I can do it.

There are no particular restrictions on the amount used, and it can be selected as appropriate; for example, the amount may be about 0.01 to about 150 parts by weight per 100 parts by weight of (5) vinyl chloride resin.

Examples of the metal powder or crushed metal foil include powders of metals such as aluminum, brass, stainless steel, lead, iron, etc. or crushed metal foils.

There are no particular restrictions on the amount to be used, and it can be selected appropriately; for example, it can be used in an amount of about 1 to about 50 parts by weight per 100 parts by weight of (4) vinyl chloride resin.

Further, as an example of the above-mentioned lubricant, any lubricant known as a lubricant for vinyl chloride resin can be used, and seven can be selected as appropriate, but examples include liquid paraffin, hydrocarbon-based lubricants such as polyethylene wax, stearic acid, Examples include fatty acid-based lubricants such as fatty acids, fatty acid amide-based lubricants, ester-based lubricants of fatty powder and alcohol, fatty alcohol-based lubricants, and polyhydric alcohol-based lubricants. The amount used can be selected as appropriate, and for example, the amount used is about 0.1 to about 10 parts by weight per 100 parts by weight of (4) vinyl chloride resin. The use of lubricants often provides favorable results in composition films of the present invention as they tend to promote dimensional stability of the film after application to a substrate.

Furthermore, examples of the above-mentioned stabilizers include, for example, calcium stearate, barium stearate, lead stearate,
Basic lead sulfite, dibasic lead phosphite, dibutyltin dilaurate, dibutyltin simalate, dibutyltin mercaptide, dioctyltin malate stabilizer ζ dioctyltin laurate stabilizer, dioctyltin mercapto stabilizer, stannane diol Examples include stabilizers such as derivatives and/or complexes thereof.

The amount used can be selected as appropriate, and for example, it can be used in an amount of about 10 parts by weight or less per 100 parts by weight of (4) vinyl chloride resin.

Furthermore, examples of the above-mentioned antifogging agent include antifogging agents such as nonionic active agent polyoxyethylene and glycerin monostearate.

The amount used can be selected as appropriate, and for example, the amount used can be about 10 parts by weight or less per 1 ρ-0 parts by weight of (4) vinyl chloride resin. Further, examples of the above-mentioned ultraviolet absorbers include, for example, hydroquinone-based hydroquinone, hydroquinone disalicylate; salicylic acid-based phenyl salicylate, paraoctylphenyl salicylate; benzophenone-based 2-hydroxy-4-methoxybenzophenone. , 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone , 2-hydroxy-4-benzoyloxybenzophenone, 2.2'-hydroxy-4-methoxypenduphenone, 2-hydroxy-4-methoxy-5-:x, sulfonepenzophenone, 2.2', 4゜4
'-Tetrahydroxybenzophenone, 2,2'-hydroxy-4,4'-dimethoxy-5-sodium sulfobenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone; Benzotriazole-2 (2/-hydroxy-5'
-methylphenyl)benzotriazole, 2 (2/-
Hydroxy-5'-methylphenyl)-5-phytoxycarbonylbenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5,6-cyclobensotriazole, 2-(2/-hydroxy-5 '-methylphenyl)-5-ethylsulfonebenztriazole,
2-(2'-hydroxy-s/fa 3-dibutylphenyl-5-chloropenttriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5') -amyl phenyl)
Penztriazole, 2-(2'-human roxy 3'
, 5'-dimethylphenyl)penztriazole, 2-
(2'-hydroxy-37,5/-dimethylphenyl)
-5-methoxypencitriazole, 2-(2'-methyl-4'-hydroxyphenyl)benzotriazole,
2-(2'-stearyloxy-3',5'-dimethylphenyl)-5-, methylbenzotriazole, 2-(
2'-Hydroxyl 5-carboxyphenyl)-benzotriazole ethyl ester, 2-(2'-hydroxy-3'-methyl-s/jg-tributylphenyl)penztriazole, 2-(2'-hydroxy-3/, 5 /
-di-tert-butylphenyl)-5-chlorpenztriazole, 2-(2'-hydroxy-5'-methoxyphenyl)benzotriazole, 2-(2'-hydroxy-
5'-phenylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-cyclohexylphenyl)benzotriazole, 2-(2'-hydroxy-5-cyclohexylphenyl)penztriazole, 2-(2 '-Hydroxy-5-cyclohexylphenyl)penztriazole, 2-(2'-human oki'/
-4',5'-diJtylphenyl)-5-carboxybenzotriazolebutyl ester 2-(2'-hydroxy-3',5'-dichlorophenyl)penztriazole, 2-(2'-hydroxy-41, s/-dichlorophenyl)benzotriazole, 2-(2'-hydroxy-3/, s/-dimethylphenyl)-5-ethylsulfonebenzotriazole, 2-(2'-hydroxy-5
'-phenylphenyl)penztria/-#, 2-(2
'-Hydroxy-4'-octoxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-methoxyphenyl)-5-methylbenzotriazole, 2-(2
'-Hydroxy-5'-methylphenyl)-5-ethoxycarbonylbenzotriazole, 2-(2'-acetoxy-5'-methylphenyl)penztriazole, 2
-(2'-hydroxy-37,S/-di-tert-butylphenyl)-5-ri00benzotriazole, 2-(2
'-Hydroxy-3/-tert-butyl-5'-methylphenyl)-5-chlorobenztriazole; substituted acrylonitriles such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, hexamethylphos-7-oli Examples include tucutriaside; )-5-chlorobenzotriazole and other benzotriazoles; 2-hydroxy-4-methoxybenzophenone 2-hydroxy-4-n-octoxybenzophenone; benzophenone-based; p-octylphenyl salicylate, phenyl salicylate and other salicylic acid derivatives; 2 -ethylhexyl-2
Examples include substituted acrylonitriles such as -cyano-3,3-diphenylacrylate, hexamethylphosphoric triamide, and the like. In the present invention, it is a preferred embodiment to use a liquid ultraviolet absorber.

Further, the amount of the ultraviolet absorber to be used can be selected as appropriate, and for example, it can be used in an amount of about 0.1 to about 10 parts ft per 100 parts by weight of the vinyl chloride resin.

In addition, antioxidants include phenol derivatives such as di-t-butyl-p-cresol, amines such as N-phenyl-N'-cyclohexylbara phenine/diamine, phenyl alpha naphthylamine, and its derivative benzimidazole. For example, inhibitors can be used.

The amount to be used can be selected as appropriate, and may be, for example, about 0.1 to about 5 parts by weight per 100 parts by weight of the captive vinyl chloride resin.

In addition, as blowing agents, azodicarbonamide, azobisisobutyronitrile, NUN'-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, p-
Examples include -p-oxybis(benzenesulfonylhydrazide)azobisinbutyronitrile, dinitrosopentamethylenetetramine, and p-toluenesulfonylhydrazide. The amount to be used is not particularly restricted and can be selected as appropriate, but for example, about 0.2 to about 15 parts by weight can be exemplified with respect to 100 parts by weight of (4) vinyl chloride resin.

Antistatic agents include polyoxyethylene alkylamine, polyoxyethylene alkyl amide, polyoxyl ethylene alkyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, alkyl sulfonate, alkylbenzene sulfonate, alkyl sulfate alkyl phosphate, quaternary ammonium chloride, Examples include quaternary ammonium sulfate.

The amount to be used is not particularly restricted and can be selected as appropriate, but for example, approximately 0.
An example may be an amount of 2 to about 10 overlapping areas.

Flame retardants include phosphate esters such as tributyl phosphate and diphenyloctyl phosphate, halogen-containing silicate esters such as tris(2,3-cypromglovir) phosphate and tris(bromochloropropyl) phosphate, chlorinated diphenyl, and tetrabromobenzene. Examples include halogen compounds, antimony-based flame retardants such as antimony trioxide, and triphenylstibine. There are no particular restrictions on the amount used, and they can be appropriately selected or used in combination. For example, the amount may be from about 0 to about 20 parts by weight per 100 parts by weight of (4) vinyl chloride resin.

Further, as other compatible resins, ethylene/viniacetate copolymer can be exemplified. The amount used is, for example, 0 to 35 parts by weight per 100 parts by weight of the captive vinyl chloride resin.
Examples include amounts in parts by weight.

The Q semi-rigid vinyl chloride resin composition of the present invention can be in the form of a molded article formed by any method known per se. For example, it can be in the form of any molded product known in the field of semi-rigid vinyl chloride resin molded products such as films (including sheets), but it can also be in the form of marking films such as those mentioned above, plastic films, plywood, metal It can be used as a film for lamination with plates, metal foils, paper, cloth, etc. In particular, it shows excellent performance as a marking film.

Molding techniques themselves are known and can be selected and used as appropriate. For example, the essential components (A), (B), and (C), and further, if desired, other additives such as those exemplified above, may be added as necessary using a ribbon blender, Henschel mixer, etc.
The mixture may be mixed using a pony mill, Teisherso, or other appropriate mixing means, and further heat-kneaded using an appropriate kneading means such as a pony mill, a kneading roll, or a Banbury mixer 1 extruder, and then used for molding. can. Examples of molding techniques include calendar molding, extrusion molding, injection molding, cast molding, and sol cast molding.

In the present invention, as the most suitable method for molding the marking film, it is preferable to use a cast molding method or a calendar molding method, and it is particularly preferable to use a cast molding method.

When using the cast molding method, the above (A),
(B), (C), if necessary, component (D), a suitable solvent, and if desired, other suitable additives such as those exemplified above are stirred and mixed to form a solution of a vinyl chloride resin composition. can be formed. Such a vinyl chloride resin composition can freely flow and give a desired shape by gravity alone, without the need to apply any particular external stress, and a solution of this desired shape can be formed into a film simply by heating and drying. to give the desired cast molded product. Examples of heating drying conditions include conditions such as about 30 to about 200° C. and about 2 to about 120 minutes. In this way, by using the cast molding method, there is no need to use an expensive large-scale molding machine, and there are advantages in that the thermal history of the resin is small. In the cast molding method, the following solvents are preferably used to dissolve the vinyl chloride resin composition and further appropriately lower the viscosity of the solution to adjust it to desired fluidity. Examples of solvents used at this time include hydrocarbons such as benzene, toluene, xylene, ethylbenzene, isoprobylbenzene, and cyclohexane; esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and butyl propionate. Class: ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate,
Ethers such as acetic acid diethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, dioxane; acetone, methyl ethyl ketone, methyl isobutyl ketone,
diisobutyl ketone, isoprobyl ketone, ethyl n
Ketones such as -butyl ketone, isophorone and cyclohexanone; halogenated hydrocarbons such as chloroform, methylchloroform, epichlorohydrin and trichlene; furans such as tetrahydrofuran and tetrahydrofurfuryl alcohol; and the like. These solvents can be used alone or in combination.

The film forming operation using the calendar forming method is well known and can be performed in the same manner in the present invention.

In the present invention, a film immediately after molding (asfo-rmed film) molded by a calendar molding machine is used.
is preferably quenched at its necking portion with a gaseous refrigerant, such as air, nitrogen, carbon dioxide, etc., at a temperature of about 30°C or less, for example from about -10°C to about 30°C.

The calender molding temperature can be, for example, about 140 to about 190°C, and when stretching is performed after molding, the temperature during stretching is about 50 to about 140°C.

The extrusion film forming operation can also be performed by means well known for producing unstretched films, and can be formed by either the T-die method or the inflation method.

As for the processing temperature, the temperatures of the cylinder part, the adapter part, and the die part may be appropriately determined between 140 and 220 DEG C. according to the capabilities of the processing machine.

To obtain a substantially unstretched film with a thickness of about 30 to 100μ, the gap between the die lips should be Q, 2' m
This method is advantageous when producing a relatively thick film of about 100 μm, since it is necessary to set the film thickness to less than / m.

Hereinafter, some embodiments of the present invention will be illustrated in more detail by giving examples. The yield stress, adhesive strength retention, printing ink adhesion, weather resistance, and workability (suitability for adhesion to curved surfaces, etc.) were measured and evaluated as follows.

(1) Yield response - sample film? :>Cut a sample for tensile test according to JIS-6734, and use this sample at a tensile speed of 200 m/min at a temperature of 23 ± 2°C and a relative humidity of 65 ± 5 yen. Perform a tensile test using a tensile tester. The tensile elongation increases as the tensile load increases, but the load (kg) at the point where the tensile load stops increasing with respect to the tensile elongation (yield point) is determined by the width of the sample before the test (IIIffll). ) x thickness (B) (Y/IIalt) is the yield stress.

(2) Adhesive strength retention An acrylic adhesive (
A sample was prepared by applying Niracera PE-121 (trade name, manufactured by Nippon Carbide Industries Co., Ltd.) to a thickness of 30 μm and laminating a silicone-coated release paper on the coated surface. This sample was heat-treated in an oven adjusted to 80±2° C. for 336 hours, and then left at room temperature for 24 hours. After this heat treatment was completed, a test piece with a width of 25 mm and a length of 200 mm was cut out. The release paper of the test piece was removed, and the test piece was adhered to the surface of a SUS 304 plate having a No. 180 Emery polishing surface using a 2 kg pressure roll.

After pasting, the specimen was left in an environment of 23 ± 2°C and relative humidity of 65 ± 5°C for 24 hours, and then gripped at one lengthwise end of the specimen and peeled off the opposite side from the gripped end at a peeling speed of 300 m/min. The force required to peel it off in the end direction (180° direction) is measured and defined as the adhesive force a (kg/crIL). The adhesive strength b (kg/c+a) was determined in the same manner using the same sample except that the heat treatment was not performed, and the adhesive strength retention rate was calculated according to the following formula.

Adhesion retention rate (A) = a/b 00L; Mino Group product), printing ink (L
Printing is performed using a 200 mesh monotetron printing screen using OV-710 Black (product of Seiko Atvans). After drying for 30 minutes in an open air conditioned at 50±3°C, 100 crosscuts with one gap were made (::ross Hatch Cutte).
r (Model: 295/1, gRIcHsEN
Nichiban cello tape is applied to this cross-cut part. Peel off the sellotape vigorously, observe with the naked eye the state of peeling of the printing ink from the film surface, count the number of peeled crosscuts out of 100 crosscuts, and evaluate according to the following evaluation criteria.

10th grade 0 9th grade 1-10 8th grade 11-20 7th grade 21-30 6th grade 31-40 5th grade 41-5゜4th grade 51-60 3rd grade 61-70 2nd grade 71-80 1st grade 91-100 ( 4) Attach the sample to a 1 m thick aluminum plate and expose it outdoors facing south at 45 degrees. After one year of outdoor exposure, the surface condition of the film was observed.

Evaluation Criteria Grade 4: Good condition with no discoloration or fading. Grade 3: There is some dirt on the film surface, but the dirt can be removed by wiping, and no discoloration or fading. Grade 3: There is some dirt on the film surface, and even if it is wiped, a faint stain remains as a stain. 2nd grade, where some dirt is visible on the film surface. 1st grade, where significant discoloration and fading is observed, with some dirt remaining on the film surface even after wiping. 1st grade, where significant discoloration and fading is observed, with most of the dirt remaining on the film surface as a stain even after wiping. ) Workability (suitability for adhesion to curved surfaces) Laminated sample used for knee contact force retention 50X
Cut into m size. After removing the release paper, the diameter is 3
The attachment of the sticker was tested at a predetermined position at the apex of a hemispherical stainless steel pole of 00n+m, and the ease of attachment and the appearance, shape, etc. of the product were evaluated based on the following evaluation criteria.

Grade 3: Easy to apply, the appearance and shape of the product are good, and no peeling occurs even after 24 hours.

Grade 2: Wrinkles or tears occur in the film during the pasting process. It is not compatible with the adherend and peels off.

Grade 1: The film stretches during the adhesion process and is difficult to apply to the adherend at a predetermined position.

In addition, the following vinyl chloride resin, ethylene vinyl ester resin, polyester plasticizer, and acrylic resin were used in the Examples and Comparative Examples.

O Ethylene/vinyl ester resin-carbon oxide monovinyl acetate-ethylene copolymer having the composition shown in Table 1.

O acrylic resin methyl methacrylate/butyl acrylate) = 85/
I 5 Number average molecular weight (Mii) 61,5 (10 Glass transition temperature Tg ('C) 65 Properties (23°C) Solid.

0 Polyester Plasticizer A polyester plasticizer consisting of a mixed alcohol of propylene glycol, butanediol and hexanediol, and adipic acid, with a number average molecular weight (M5) of about 3000.

Examples 1 to 15 and Comparative Examples 1 to 6 5G-1100N, manufactured by Nippon Cavide Co., Ltd., average degree of polymerization of about 1100], polyester plasticizer, ethylene/vinyl ester resin, acrylic resin, and Al paste. In addition to containing the amounts shown in Table 1, 1. BaZZn stabilizer (A
P-539; 3.0 parts by weight, 1 part by weight, manufactured by Adeka Argus Chemical Co., Ltd.) Ester-based lubricant (Bu-8t; 0.5 parts by weight, manufactured by Fine Chemical Co., Ltd.) Benzotriazole-based ultraviolet absorber 2 parts by weight (Tinupin P; Ciba Geigy Co., Ltd. product) The mixed resin components were processed using a prescribed processing method to produce a film with a thickness of 50μ, and the physical properties of the obtained film were measured using the method described above, and the results are shown in Table 1 below. Indicated.

(1) Casting method Tetrahydrofuran was added so that the resin concentration of the mixed resin component was 200 parts by weight, and the mixture was stirred and dissolved in a closed container at 100° C. for 2 hours to obtain a resin solution composition.

After the resin solution composition was cooled and degassed using a caster, it was cast onto a stainless steel plate using casters, dried with hot air at 140° C. for 15 minutes, and peeled off to obtain a dried film with a thickness of 50 μm.

(11) Calender method The mixed resin components are heated to 100°C using a ribbon blender.
30 molecules were prepared and kneaded, and then 150 molecules were prepared using two rolls.
'C1 was melt-kneaded for 10 minutes, and a film with a thickness of about 50 μm was obtained using four inverted calender rolls at a roll temperature of 175 to 180°C.

Claims (1)

[Claims] 1. (B) A liquid polyester having a number average molecular weight (Mn) of about 1,500 or more, based on 100 parts by weight of a vinyl chloride resin containing 0 to about 20% by weight of a copolymer component. about 1 to about 20 parts by weight of a vinyl chloride resin plasticizer, O to about 10 parts by weight of other vinyl chloride resin plasticizers, and 1 to 0 parts of an ethylene/saturated carbo/acid vinyl ester goo oxide carbon based copolymer resin. About 45 to about 350% by weight of an ethylene/vinyl ester resin having a 10-bond in the main chain, based on the total amount of the plasticizer (B).
, and the yield stress is 1 to 6 kli'/
1 m''. 2. The semi-rigid vinyl chloride resin molding composition according to claim 1, wherein the semi-rigid vinyl chloride resin molding composition is a marking film molding composition. Vinyl chloride resin molding composition. 3. The liquid polyester plasticizer is a liquid polyester plasticizer derived from a dibasic acid having 4 to 15 carbon atoms and a dihydric alcohol having 2 to 20 carbon atoms. A semi-rigid vinyl chloride resin molding composition according to scope 1 or 2. 4. The composition has a number average molecular weight (Mn) of about 1.500.
~50,000 and solid at 23°C, in an amount up to about 20% by weight based on (4) the vinyl chloride resin. Or the semi-rigid vinyl chloride resin molding composition according to item 2. 5. Claim 1 or 2, wherein the semi-rigid vinyl chloride resin molding composition further contains an ultraviolet absorber.
The semi-rigid vinyl chloride resin molding composition described in 1. 6. The semi-rigid vinyl chloride resin molding composition according to claim 1 or 2, wherein the yield stress is 1 to 5 to 9/llll112.