JPH0548255B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is suitable for molding semi-hard vinyl chloride resin molded products such as films, sheets, overlay films, and laminating films, and is particularly suitable for use as a marking film molding composition. The present invention relates to a molding composition. More specifically, the adhesiveness of the pressure-sensitive adhesive when a pressure-sensitive adhesive layer is provided on a film of the composition, is flexible and has a yield stress of 1 to 6 Kg/mm ² and has an appropriate stiffness. In terms of properties such as force retention, adhesion between printing ink and film when printing on the film, weather resistance, suitability for adhesion to curved surfaces when used as a marking film, and ultraviolet absorber retention, The present invention relates to an improved semi-rigid vinyl chloride resin molding composition that has both of these excellent properties. In particular, the present invention provides (A) 100 parts by weight of a vinyl chloride resin containing 0 to about 20% by weight of a copolymer component, and (B) a liquid polyester system having a number average molecular weight (n) of about 1500 or more. About 1 to about 20 parts by weight of a plasticizer, 0 to about 10 parts by weight of another plasticizer for vinyl chloride resin, and (C) ethylene/vinyl ester of saturated carboxylic acid/carbon monoxide copolymer resin. in the main chain

[Formula] Ethylene/vinyl ester resin having a bond is approximately
45 to about 350% by weight; and (D) a number average molecular weight (n) of 1,500 to 50,000;
Low molecular weight acrylic or methacrylic resins that are solid at 23°C, excluding acrylic or methacrylic graft copolymer resins, as described in (A) above.
5 to about 20% by weight based on the vinyl chloride resin, and having a yield stress of 1 to 6 kg/mm 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. Accordingly, resins exhibiting a wide range of physical properties ranging from rubber-like elastic bodies to rigid bodies are put to practical use in various applications. Furthermore, it is generally known that various acrylic resins are blended with vinyl chloride resin for the main purpose of improving processability during molding. 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 troubles caused by or related to 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 conducted research 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 (n ) about 1 to about 20 parts by weight of a liquid polyester plasticizer that satisfies the conditions, and (C) in the main chain consisting of ethylene/vinyl ester of saturated carboxylic acid/carbon monoxide copolymer resin.

[Formula] An ethylene/vinyl ester resin having a bond that satisfies a bond parameter of about 45 to about 350% by weight based on the total amount of plasticizer (B) and has a yield stress of 1 to 6 Kg/mm ² By satisfying the bonding requirements of the composition, flexibility with appropriate stiffness and adhesive strength retention of the pressure-sensitive adhesive when the pressure-sensitive adhesive layer is provided on the film of the composition. This film has excellent properties in terms of adhesion between printing ink and film when printing is performed, weather resistance, suitability for adhesion to curved surfaces when used as a marking film, and ultraviolet absorber retention. The present inventors have discovered that it is possible to provide a semi-rigid vinyl chloride resin molding composition that has both the excellent properties desired in a marking film molding composition. For example, motorcycles, four-wheelers, and other various vehicles,
Striped stickers for decoration or display of various land and sea containers, vehicles such as yachts, boats, and other vessels, as well as furniture, door boards, window frames, pillars, and other building materials; Advertising stickers used to display advertising characters, figures, patterns, etc. on billboards and advertising boards; Various display stickers for traffic signs, road signs, information boards, hazard prevention signs, product marks, etc. Marking films are used in a wide range of fields such as; Such marking films are, for example,
It is used in such a manner that a suitable pressure sensitive adhesive layer is provided on one side, and a suitable release paper is attached on the adhesive layer, and when used, the release paper is peeled off and the desired part of the desired base material is attached. It is used in an adhesive manner. However, with conventional marking films, there has been a problem in that the plasticizer in the film bleeds out into the adhesive layer, reducing its adhesive strength over time and worsening its adhesive strength to the base material. 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, there is a problem with conventional marking films in that the adhesion between the printing ink and the film is insufficient and the film easily peels off.
The suitability for adhesion to curved surfaces was also unsatisfactory. Furthermore, since marking films are often used outdoors, it is common to include UV absorbers in them, but in conventional marking films, UV absorbers tend to evaporate due to heat during film molding.
Such films also had the 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, the above-mentioned plasticizer bleed-out or bleed-out 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 portion 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 flexibility and appropriate stiffness. According to research by the present inventors, up to about 5 parts by weight of other plasticizers for vinyl chloride resin may be used in combination with 100 parts by weight of the vinyl chloride resin (A).
about 1 to about 20 parts by weight of a liquid polyester plasticizer that satisfies the number average molecular weight (n) condition in a specific range;
and (C) in the main chain consisting of ethylene/vinyl ester of saturated carboxylic acid/carbon monoxide copolymer resin.

[Formula] Ethylene/vinyl ester resin having a bond is approximately
45 to about 350% by weight and the low molecular weight (meth) of (D) above
By satisfying the bonding requirements of the acrylic resin to have a bonding parameter of about 5 to about 20% by weight based on the vinyl chloride resin of (A) and a yield stress of 1 to 6 Kg/ ^mm2 , The above-mentioned difficulties have been overcome, and as will be shown experimentally later by giving examples and many comparative examples, a semi-rigid vinyl chloride resin molding composition, especially a marking film molding resin, has excellent improved properties. It has been discovered that compositions and shaped 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 vinyl chloride resin molding composition of the present invention, there are no particular restrictions on the molding method, and there is no particular restriction 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 components of the composition are dispersed in a sol state, which is then cast and hot-melted. Molding methods such as the sol cast method can be used to obtain a film. In general, films produced by the casting method are particularly preferable compared to the thermal processing method in that they have less distortion. There are no particular restrictions on the vinyl chloride resin (A) 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,
Degree of polymerization from about 600 to about 3000, preferably from about 700 to about
Examples include vinyl chloride resins having a polymerization degree of about 2000, more preferably about 800 to about 1800, particularly preferably about 1200 to about 1600. Furthermore, the vinyl chloride resin (A) can also be a resin for vinyl chloride paste. The vinyl chloride resin (A) above is a copolymer containing a vinyl chloride homopolymer and a copolymer component up to about 20% by weight, preferably about 10% by weight, particularly preferably about 6% by weight. Something can happen. Examples of such copolymer components include vinyl monomers,
For example, olefinic monomers such as ethylene, propylene, butylene, isobutylene, etc., dienes such as butadiene, chlorobutadiene, pentadiene, etc., and vinyl acetylene derivatives. For example, vinyl halide monomers such as vinyl fluoride, vinylidene chloride, vinyl bromide, etc. For example, (meth)acrylic acid ester monomers such as ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, propyl methacrylate, ethylene glycol dimethacrylate, and the like. For example, vinyl ester monomers such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate, and the like. For example, methyl vinyl ether, propyl vinyl ether,
Vinyl ether monomers such as butyl vinyl ether, phenyl vinyl ether, allyl vinyl ether, etc. Styrene, methylstyrene, dimethylstyrene, vinylstyrene, chlorstyrene,
Examples include copolymers of styrene derivatives such as vinylphenol and the like. The vinyl chloride resin (A) as 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, Yuka Vinyl SG-700, SG-800, SG-
1100, SG-1300, SG-1400 [vinyl chloride resin,
Ryoichi Co., Ltd. product or Nippon Carbide Industries Co., Ltd. product], Zeon 121, Zeon 131, Zeon 25, Zeon 135J [vinyl chloride resin, Nippon Zeon Co., Ltd. product], Vinica 51ME, Vinica P-440, Vinica P
Examples include commercially available vinyl chloride resins such as -400 [vinyl chloride resin, manufactured by Mitsubishi Monsite Co., Ltd.] and Sumiritz PX [vinyl chloride resin, manufactured by Sumitomo Chemical Co., Ltd.]. The (B) plasticizer used in the semi-rigid vinyl chloride resin molding composition of the present invention is the above-mentioned (A) vinyl chloride resin.
For 100 parts by weight, the number average molecular weight (n) is approximately
1500 or more, preferably about 1500 to about 6000, more preferably about 1500 to about 4000, more preferably about 2000 to about
about 1 to about 20 parts by weight of 4000 polyester plasticizer,
Preferably from about 1 to about 15 parts by weight, more preferably from about 2 to about 10 parts by weight, and from 0 to about 10 parts by weight of other vinyl chloride resin plasticizers. Examples of such liquid polyester plasticizers include one to three types selected from _C4 to _C15 dibasic acids such as maleic acid, adipic acid, phthalic acid, azelaic acid, and sebacic acid; Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, dipropyl glycol, 1,6
-hexanediol, 2,24-trimethyl 1,3
- 1 to 5 types selected from C ₂ to C ₂₀ dihydric alcohols such as pentanediol, 1,5-pentanediol, etc. and acetic acid, coconut oil fatty acid, etc.
Examples include liquid polyester plasticizers obtained by reacting a chain stopper appropriately selected from n-octyl alcohol and n-decyl alcohol. Among these, one or two selected from adipic acid, phthalic acid, maleic acid, propylene glycol, dipropylene glycol,
A preferred example is a liquid polyester plasticizer derived from one to three selected from hexanediol and butanediol. What is the liquid state of the liquid polyester plasticizer of the present invention?25
It means a viscous liquid whose viscosity at °C is 500,000 poise or less as measured by a BH type rotational viscometer, and the number average molecular weight (n) of the polyester plasticizer is GPC (Gel,
This is the value measured using the Permeation Chromatography (Permeation Chromatography) 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 PN-150, PN-260, PN-446 (polyester plasticizer, manufactured by Adeka Argus Chemical Co., Ltd.), and NS-3700 (polyester plasticizer, manufactured by Dainichiseika Chemical Co., Ltd.). Kogyo Co., Ltd. product), P-204N, P-29 (polyester plasticizer, Dainippon Ink & Chemicals Co., Ltd. product), G-25, G-40 (polyester plasticizer, Rohm & Haas product), SP −171, DIDA,
SP-501, SP-115S (polyester plasticizer, Sanken Kako Co., Ltd. product), Kodaflex NP-10 (polyester plasticizer, Eastman Chemical
Products), Flexol R-2H (polyester plasticizer, Union Carbide Corp. product),
Edenol1200 (polyester plasticizer, Henkel product), Rheoplex100, Rheoplex110,
Rheplex220 (polyester plasticizer, Ciba-
Geigy products), etc. can be exemplified. 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, a small amount of other vinyl chloride resin plasticizers, preferably up to about 10 parts by weight, preferably up to about 5 parts by weight, can be used in combination with 100 parts by weight of (A) vinyl chloride resin. . Examples of such other plasticizers for vinyl chloride resins include C ₁ -C ₃₅ mono- or poly-basic carboxylic acids _.
Esters of C ₃₅ monohydric or polyhydric alcohols and oxiranes Oxygen content 2-9 mol% Molecular weight approx.
2000 or less, for example from about 10 to about 2000, may be mentioned. Such other plasticizers for vinyl chloride resins can be exemplified. For example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-(-ethylhexyl) phthalate, di-n-octyl phthalate, higher alcohol phthalate, diisooctyl phthalate, diisobutyl phthalate,
Dipentyl phthalate, diisodecyl furatate, ditridecyl phthalate, diundecyl phthalate, di(heptylnonylundecyl) phthalate, benzyl phthalate, butylbenzyl phthalate, dinonyl phthalate, di-n/isoalkyl C ₁ -C ₃₅ monohydric or polyhydric alcohol esters of phthalic acid such as phthalate; e.g. dimethyl isophthalate, di-(2-ethylhexyl)-isophthalate, diisooctyl isophthalate, polyalkylene glycol isophthalate C ₁ -C ₃₅ monohydric or polyhydric alcohol esters of isophthalic acid such as;
(2-ethylhexyl)tetrahydrophthalate,
_C1 - _C35 monohydric or polyhydric alcohol esters of tetrahydrophthalic acid such as di-n-octyltetrahydrophthalate, diisodecyltetrahydrophthalate, _C7 - _C10 alkyltetrahydrophthalate; for example, di-n-butyl adipate, di-(2-ethylhexyl)adipate,
C ₁ to _{C 35} monohydric or polyhydric alcohol esters of adipic acid such as diisodecyl adipate, benzyl octyl adipate, di-(butoxy ethoxyethyl) adipate;
(2-ethylhexyl) azelate, diisooctyl azelate, di-2-ethylhexyl-4
- C ₁ of azelaic acid such as thioazelate etc.
Monohydric or polyhydric alcohol esters of C ₃₅ ; e.g. di-n-butyl sebacate, di-(2
C ₁ -C ₃₅ monohydric or polyhydric alcohol esters of sebacic acid such as -ethylhexyl) sebacate, etc.; e.g. di-n-butyl malate,
C ₁ -C ₃₅ monohydric or polyhydric alcohol esters of maleic acid such as dimethyl maleate, diethyl maleate, etc.; fumaric acids such as di-n-butyl fumarate, di-(2-ethylhexyl) fumarate, etc. C ₁ -C ₃₅ monohydric or polyhydric alcohol esters of acids; for example, tri-(2-
C ₁ -C ₃₅ monohydric or polyhydric alcohol esters of trimellitic acid such as ethylhexyl) trimellitate, tri-n-octyl trimellicate, triisodecyl trimellitate, etc.; for example, triethyl citrate, tri-n-butyl citrate, acetyl citrate; _-C1 -C35 monohydric or polyhydric alcohol esters of citric acid, such as triethyl citrate; for example, _C1 - _C35 of itaconic acid, such as _monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, etc. No. 1
hydric or polyhydric alcohol esters; e.g.
C ₁ -C ₃₅ monohydric or polyhydric alcohol esters of oleic acid such as butyl oleate, tetrahydrofurifuryl oleate, glyceryl monooleate, etc.; for example, methyl acetylsinolate,
C ₁ to C ₃₅ monohydric or polyhydric alcohol esters of ricinoleic acid such as butylacetyl ricinoleate, glyceryl monoricinolate, etc.; such as n-butyl stearate, glyceryl monostearate, diethylene glycol distearate, etc. C ₁ - C ₃₅ monohydric or polyhydric alcohol ester of stearic acid; other diethylene glycol monolaurate, benzenesulfone butyramide, trimethyl phosphate, tributoxyethyl phosphate, tetra-2-ethylhexyl pyromellitate, diethylene glycol di Benzoate, glycerol monoacetate, chlorinated paraffin, oxirane Epoxy derivative with an oxygen content of 2-9% and a molecular weight 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/monomer as essential components together with the above-mentioned (A) vinyl chloride resin and (B) liquid polyester plasticizer. In the main chain consisting of carbon oxide copolymer resin

[Formula] About 45 to about 350% by weight of ethylene/vinyl ester resin having a bond, based on the total amount of plasticizer (B) above,
Preferably, the content is about 50 to about 300% by weight. Ethylene/third monomer/carbon monoxide copolymer resins that can include the above copolymer resin (C) used in the composition of the present invention and their production methods are known (for example, Japanese Patent Publication No. 55 -50063; JP-A-48-26228),
Furthermore, the above-mentioned materials are commercially available (e.g., "Elvaloy", a product of DuPont USA), and in the present invention, the above-mentioned
You can select and use the one that satisfies the requirements specified in (C). 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 does not include the specific liquid polyester plasticizer of (B) and the bonding parameters of (A), (B), and (C) specified in the present invention. Regarding the bonding parameters with the specific copolymer resin of (C), and further regarding the existence of the technical problems in the marking film described above and the excellent effects of the composition of the present invention achieved by overcoming the problems, It is not mentioned or suggested at all. In the composition of the present invention, as the copolymer resin (C),
Among the above-mentioned known resins, in the main chain consisting of ethylene/vinyl ester of saturated carboxylic acid/carbon monoxide copolymer resin,

[Formula] An ethylene/vinyl ester resin having a bond is selectively used. Examples of vinyl esters of saturated carboxylic acids include vinyl esters of _C2 to _C19 saturated carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate. Among these, vinyl esters of _C2 - _C4 saturated carboxylic acids, such as vinyl acetate and vinyl propionate, are more preferred. The copolymer resin is in the main chain.

[Formula] This bond can be detected as an absorption around 1715 cm ^-1 in the infrared absorption spectrum (IR). In addition, these vinyl esters are
In 1R, there is a side chain near 1735 cm ^-1.

[Formula] usually indicates a bond. The composition range of ethylene, vinyl ester of saturated carboxylic acid, and carbon monoxide of the copolymer resin (C) to be used can be appropriately selected within a fairly wide range, but for example, (a) 20 to 94% by weight of ethylene, ( b) Vinyl ester of saturated carboxylic acid 5-50
and (c) 1 to 30% by weight of carbon monoxide; preferably (a) 40 to 82% by weight, (b) 15 to 40% by weight, and (c) 3 to 30% by weight.
20% by weight; more preferably (a) 55-75% by weight, (b)
a composition range of 20 to 30% by weight and (c) 5 to 15% by weight,
I can give an example. As explained in detail above, the semi-rigid vinyl chloride resin molding composition of the present invention contains (A) 0 to about 20% by weight, preferably 0 to about 10% by weight, more preferably 0 to about 6% by weight. (B) Number average molecular weight (n) is 1500 or more, preferably about 1500 to about 6000, more preferably about 1500 to about
from about 1 to about 20 parts by weight, preferably from about 1 to about 15 parts by weight, preferably from about 2 to about 4000, more preferably from about 2000 to about 4000,
10 parts by weight, and 0 to about 10 parts by weight, preferably 0 to about 5 parts by weight, of another plasticizer for vinyl chloride resin, and (C) ethylene/vinyl ester of saturated carboxylic acid/carbon monoxide based copolymer. In the main chain consisting of resin

[Formula] Ethylene/vinyl ester resin having a bond is approximately
45 to about 350% by weight, preferably about 50 to about 300% by weight; and (D) a number average molecular weight (n) of 1500 to 50000;
Low molecular weight acrylic or methacrylic resins that are solid at 23°C, excluding acrylic or methacrylic graft copolymer resins, as described in (A) above.
from about 5 to about 20% by weight based on the vinyl chloride resin, and has a yield stress of from 1 to 6 Kg/ ^mm2 , preferably from 1 to 5, more preferably from 1.2 to 4.5 Kg/ ^mm2.
It is. By satisfying the above bonding requirements, the composition of the present invention has flexibility with appropriate stiffness, and the adhesive strength of the adhesive when a pressure-sensitive adhesive layer is provided on the composition film. retention, adhesion between printing ink and film when printing is performed on the film, weather resistance under outdoor usage conditions, suitability for adhesion to curved surfaces when used as a marking film, and ultraviolet absorber retention. It has both excellent characteristics such as gender. It is presumed that the above-mentioned components (A), (B), and (C) as well as the component (D) mutually influence each other for the combination of the above-mentioned excellent properties in the composition of the present invention. Although it is difficult to unambiguously state the effect of each parameter, as will be shown experimentally later with many comparative examples and examples, if the coupling requirements specified in the present invention are deviated from, the present invention In practice, it is extremely difficult to achieve a combination of the above-mentioned excellent properties in a composition. When the vinyl chloride resin (A) contains a copolymer component, the amount of the copolymer component is up to about 20% by weight,
Preferably about 10% by weight, more preferably about 6% by weight
That's it. If the amount of the copolymerized component exceeds the above amount, it tends to cause disadvantages such as a decrease in thermal stability and coloring of the film, so it should be used in an amount of about 20% by weight or less. It is better. In addition, the degree of polymerization of (A) 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 800
~ about 1800, particularly preferably about 800 to about 1600, for example, has good solubility in the solvent used when employing the solution casting method, has excellent viscosity characteristics (salivability), and, for example, It is convenient to use (A) vinyl chloride resin having a degree of polymerization as exemplified above, since more favorable results can be obtained in terms of good heat stability and meltability when the calendering method is employed. The number average molecular weight (n) of the polyester plasticizer (B) is about 1500 or more, preferably about 1500 to about
6000, more preferably in the range of about 1500 to about 4000, furthermore in the range of about 2000 to about 4000, particularly in the range of about 2000 to about 3200. If the value is too low, below about 1500, the tendency of plasticizer bleed-out, combined with the other requirements of (A) and (C), will be disadvantageously increased, adhesion retention, weather resistance, ultraviolet absorbency, etc. This causes non-negligible deterioration in terms of retention, etc. On the other hand, if a solid polyester plasticizer is used in place of a liquid polyester plasticizer, the elongation of the film will be reduced and the film will become undesirably brittle. Therefore, as the liquid polyester plasticizer (B), a polyester plasticizer satisfying the above number average molecular weight (n) condition is selected and used. Furthermore, the amount of the liquid polyester plasticizer (B) used is about 1 to 1 to 100 parts by weight of the vinyl chloride resin (A).
About 20 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 deviates from the above range, the amount is too small. If it is too much, the film tends to lose its appropriate flexibility due to the combination requirements of (A) and (C), which is disadvantageous, and if it exceeds the above range, it is too excessive. , the adhesive strength decreases,
Furthermore, the adhesion between the printing ink and the film, weather resistance, ultraviolet absorber retention, etc. are also deteriorated.
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 about 10 parts by weight, preferably up to about 5 parts by weight, based on 100 parts by weight of (A) vinyl chloride resin. . 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 absorbing properties will increase. This is undesirable in that it causes deterioration in retention properties and the like. The amount of the ethylene/vinyl ester resin (C) is about 45 to about 350% by weight, preferably about 50 to about 300% by weight, based on the total amount of the plasticizer (B). If the amount of component (C) used is too small and deviates from the above range, the appropriate flexibility of the film will be impaired in combination with other requirements, resulting in poor film quality and wrinkles. However, when used as a marking film, the suitability for adhesion to curved surfaces tends to decrease, and if the above range is exceeded, the film becomes soft and stretches, making it difficult to work when used as a marking film. Sexuality becomes worse.
Furthermore, printing ink adhesion and weather resistance also tend to decrease. The semi-rigid vinyl chloride resin molding composition of the present invention contains (A), (B) and (C) under conditions that satisfy the above bonding requirements, and has a yield stress of 1 to 6 kg/
mm ² , preferably 1 to 5 Kg/mm ² , more preferably
Satisfies the requirements of 1.2~4.5Kg/ ^mm2 . 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 temperature 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 stick it 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 (D) a number average molecular weight (
n) is about 1,500 to about 50,000 and is solid at 23°C.
(A) In an amount from about 5% to about 20% by weight based on the vinyl chloride resin. The inclusion of component (D) further improves adhesive strength retention and further improves weather resistance, which is preferable. Such (D) low molecular weight acrylic or methacrylic resin has a number average molecular weight (n) of approximately
Low molecular weight acrylic resins having a molecular weight of 1,500 to about 50,000, preferably about 2,000 to about 40,000, more preferably about 2,500 to about 30,000 and solid at 23°C are available. It may be utilized in an amount of from about 5% to about 20% by weight, preferably from about 5% to about 15%, more preferably from about 7% to about 12% by weight, based on (A) vinyl chloride. As the (D) solid low molecular weight acrylic or methacrylic resin, any low molecular weight acrylic resin that satisfies the above number average molecular weight (n) condition and is solid at 23°C can be used. Preferred acrylic resins include at least one type of acrylic or methacrylic acid alkyl ester selected from the group consisting of C ₁ -C ₁₈ alkyl esters of acrylic acid and C ₁ -C ₁₈ alkyl esters of methacrylic acid; Examples include low molecular weight acrylic resins that are homopolymers and copolymers that may contain polymerizable components, satisfy the above number average molecular weight (n) conditions, and are solid at 23°C. Specific examples of the _C1 - _C18 alkyl ester of acrylic acid and the _C1 - _C18 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.Chloropropyl acrylate Dimethylaminoethyl acrylate Diethylaminoethyl acrylate Glycidyl acrylate 2-Chloroethyl acrylate 2-3 dibromopropyl acrylate Tribromophenylacrylate Allyl acrylate Oleyl acrylate Epoxystearyl acrylate Polyethylene glycol diacrylate Hexane glycol diacrylate Neopentyl glycol diacrylate Dipropylene glycol diacrylate Trimethylolpropane triacrylate Tetramethylolmethane Triacrylate 2-methyl-3-sulfopropylacrylamide Calcium diacrylate Magnesium diacrylate Barium diacrylate Zinc diacrylate Aluminum triacrylate Lead diacrylate Sodium acrylate Methacrylate Methyl methacrylate Ethyl methacrylate Propyl methacrylate iso-propyl methacrylate n-butyl methacrylate iso・Butyl methacrylate Tertiary butyl methacrylate Cyclohexyl methacrylate Octyl methacrylate 2.Ethylhexyl methacrylate Lauryl methacrylate Stearyl methacrylate Methoxyethyl methacrylate Ethoxyethyl methacrylate Butoxyethyl methacrylate Methoxypolyethylene glycol 2.Hydroxyethyl methacrylate 2.Hydroxypropyl methacrylate 2.Hydroxy 3.Chloropropyl methacrylate Polypropylene glycol monomethacrylate Dimethylaminoethyl methacrylate Diethylaminoethyl methacrylate Glycidyl methacrylate Tetrahydrofurfuryl methacrylate 2-chloroethyl methacrylate Allyl methacrylate Oleyl methacrylate Epoxystearyl methacrylate Ethylene glycol dimethacrylate Polyethylene glycol dimethacrylate Butylene glycol dimethacrylate Hexane glycol dimethacrylate Neopentyl glycol dimethacrylate Methacrylates include polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and the like. The solid low molecular weight acrylic resin (D) may further contain other copolymerizable components. The content can be changed and selected as appropriate within a range such that the solid acrylic resin (D) satisfies the number average molecular weight (n) condition. For example, for 100 parts by weight of acrylic ester or methacrylic ester, about 100 parts by weight or less, preferably about
Examples include amounts such as 30 parts by weight or less. Examples of such other copolymerizable components (or modifying monomers) include olefinic monomers such as ethylene, propylene, butylene, and isobutylene; dienes such as butadiene, chlorobutadiene, and pentadiene, and vinyl acetylene; Derivatives; vinyl ester monomers such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate; vinyl or vinylidene monomers such as vinyl chloride and vinylidene chloride; for example, methyl vinyl ether; propyl vinyl ether and butyl vinyl ether・Vinyl ether monomers such as phenyl vinyl ether; styrene, methylstyrene,
Styrene derivatives such as dimerthystyrene 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 chloride, acrylonitrile Examples of copolymerizable components include other acrylic monomers such as , acrylamide, and N-tert-butylacrylamide. Component (D) that can be used in the present invention is a low molecular weight acrylic or methacrylic resin that has a number average molecular weight (n) of about 1,500 to about 50,000 and is solid at 23°C. Advantageously, the transition temperature (Tg) is preferably 30°C or higher, more preferably 35°C or higher. Here, the glass transition temperature (Tg) is "Mechanical Properties of Polymers" by LE Nielsen, translated by Nobuharu Onogi.
(April 15, 1965, published by Kagaku Dojinsha) means the Tg measured and determined by the method described on pages 11 to 35 of the same book, and in the case of copolymers, the method described on pages 26 to 27 of the same book. means the Tg calculated and determined by That is, the Tg of the copolymer was calculated using the following formula. 1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+W _o /Tg _o (however, W ₁ + W ₂ +... W _o = 1) In the above formula, Tg is the copolymer glass transition temperature and is an absolute Calculate by converting it to temperature. Tg ₁ , Tg ₂ ... and _Tgo are the glass transition temperatures of pure homopolymers 1, 2 ... and n for each monomer component 1, component 2 ... and component n constituting the copolymer, Calculate by converting to absolute temperature.
W ₁ , W _{2 .} . . and W _o are the weight fractions of the respective components constituting the copolymer in the copolymer. Homopolymer for each monomer component above
Tg(〓) is known and is 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−
When the Tg of the resin obtained from BMA-BA (60% by weight - 30% by weight - 10% by weight) is calculated, it becomes 0.6/376 + 0.3/294 + 0.1/216 = 1/Tg, and Tg = 325〓.

[Table] The number average molecular weight (n) of the low molecular weight acrylic or methacrylic resin (D) that is solid at 23°C that can be used in the composition of the present invention is about 1,500 to about 50,000, preferably about 2,000 to about 40,000. . If it deviates from the above range and is too small, under the combination requirements with other requirements of (A) and (B), especially as a combination parameter with (B),
The tendency of the plasticizer in requirement (B) to bleed out increases significantly, resulting in non-negligible deterioration in terms of adhesive strength retention, weather resistance, etc. Furthermore, the (D) low molecular weight acrylic resin itself tends to bleed out, and this tendency does not meet the solid requirements at 23°C and at 25°C.
In the case of liquid low-molecular-weight acrylic resins, this increases further, causing a film surface bleed phenomenon, which further worsens adhesive strength and weather resistance, and is also disadvantageous in terms of UV absorber retention. accompanied by. Furthermore, the number average molecular weight (
If n) deviates from the above range and becomes too large, the appropriate flexibility of the film will be impaired, and the film will not have adequate flexibility under the combination requirements with the other requirements of (A) and (B). There is a tendency for the advantages to be lost, and furthermore, there is a tendency for the low molecular weight acrylic resin (D) to decompose and discolor when molded into a film structure by, for example, a calendaring method. Therefore, when using the resin (D), it should be within the above number average molecular weight (n) range and
A solid low molecular weight acrylic resin at 23°C should be selected. The amount of the (D) low molecular weight acrylic or methacrylic resin used is up to about 20% by weight based on the (A) 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 (D) low molecular weight acrylic or methacrylic resin is used, the amount used should be appropriately selected within about 20% by weight based on the above (A) vinyl chloride resin. . 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, metal powders, crushed metal foil powders, lubricants, stabilizers, antifogging agents, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, and foaming agents. Examples include agents. Examples of the above colorants include titanium oxide, zinc white, lead white, calcium carbonate, gypsum, precipitated silica, carbon black, red iron oxide, mica, molybdenum red, cadmium yellow, yellow lead, titanium yellow, chromium oxide green, and ultramarine blue. Inorganic pigments such as Permanent Red 4R Hansa Yellow 10G, Benjiji Yellow
Examples include organic pigments such as GR. Permanent Carmine FB, Phthalocyanine Blue B, and Phthalocyanine Green. The amount to be used is not particularly restricted and can be selected as appropriate, but for example, it can be used in an amount of about 0.01 to about 150 parts by weight per 100 parts by weight of the (A) vinyl chloride resin. Examples of the metal powder or crushed metal foil include metal powders or crushed metal foils such as aluminum, brass, stainless steel, lead, and iron. There are no particular restrictions on the amount 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 the vinyl chloride resin (A). Further, as an example of the above-mentioned lubricant, any lubricant known as a lubricant for vinyl chloride resin can be used, and can be selected and used as appropriate. 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 acids and alcohols, fatty alcohol-based lubricants, and polyhydric alcohol-based lubricants. The amount to be used can be selected as appropriate, and for example, about 0.1 to about 10 parts by weight can be exemplified based on 100 parts by weight of the (A) vinyl chloride resin. The use of lubricants often provides favorable results in composition films of the present invention, which 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 dimalate, dibutyltin mercaptide, dioctyltin. Examples include stabilizers such as chloride stabilizers, dioctyltin laurate stabilizers, dioctyltin mercapto stabilizers, stannane diol derivatives, and/or complexes thereof. The usage amount can be selected as appropriate, but for example,
(A) An example of an amount of about 10 parts by weight or less per 100 parts by weight of 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 100 parts by weight of (A) vinyl chloride resin. Further, examples of the above-mentioned ultraviolet absorbers include, for example, hydroquinone series - hydroquinone, hydroquinone disalicylate; salicylic acid series - phenyl salicylate, paraoctylphenyl salicylate; benzophenone series - 2-hydroxy-4-methoxy Benzophenone, 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-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzo Phenon, 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-
Butoxycarbonylbenzotriazole, 2-
(2'-hydroxy-5'-methylphenyl)-5,6
-dichlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5-ethylsulfonebenzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-
(2'-hydroxy-5'-amylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dimethylphenyl)benzotriazole, 2-
(2'-hydroxy-3',5'-dimethylphenyl)-
5-methoxybenzotriazole, 2-(2'-methyl-4'-hydroxyphenyl)benzotriazole, 2-(2'-stearyloxy-3',5'-dimethylphenyl)-5-methylbenzotriazole,
2-(2'-hydroxy-5'-carboxyphenyl)
-benzotriazole ethyl ester, 2-
(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-
Chlorbenzotriazole, 2-(2'-hydroxy-5'-methoxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-phenylphenyl)-5-chlorobenzotriazole, 2-(2'-
Hydroxy-5'-cyclohexylphenyl)benzotriazole, 2-(2'-hydroxy-5-
cyclohexyl phenyl)benzotriazole,
2-(2'-hydroxy-5-cyclohexylphenyl)benzotriazole, 2-(2'-hydroxy-4',5'-dimethylphenyl)-5-carboxybenzotriazole butyl ester, 2-
(2'-hydroxy-3',5'-dichlorophenyl)benzotriazole, 2-(2'-hydroxy-4',
5′-dichlorophenyl)benzotriazole, 2
-(2′-hydroxy-3′,5′-dimethylphenyl)
-5-ethylsulfonebenzotriazole, 2-
(2'-hydroxy-5'-phenylphenyl)benzotriazole, 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)benzotriazole, 2
-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-
(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole; substituted acrylonitriles such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, hexamethylphosphoric Triaside; etc. are exemplified, preferably 2-(2'-hydroxy-5'-methyl-phenyl)
Benzotriazole, 2-(2'-hydroxy-
Benzotriazoles such as 3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, etc. Benzophenones; salicylic acid derivatives such as p-octylphenyl salicylate and phenyl salicylate; substituted acrylonitriles such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, hexamethylphosphoric triamides,
etc. 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, about 0.1 to about 10 parts by weight can be exemplified with respect to 100 parts by weight of the vinyl chloride resin (A). Also, as an antioxidant, di-t-butyl-p-
Examples include phenol derivatives such as cresol, amines such as N-phenyl-N'-cyclohexyl para-phenylenediamine, phenyl-alphanaphthylamine, and antioxidants such as benzimidazole, a derivative thereof. The amount used can be selected as appropriate, and for example, about 0.1 to about 5 parts by weight can be exemplified based on 100 parts by weight of the (A) vinyl chloride resin. Further, as blowing agents, azodicarbonamide, azobisisobutyronitrile, N,N'-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, pp-oxybis(benzenesulfonylhydrazide)azobisisobutyronitrile, dinitrosopentamethylenetetramine,
Examples include p-toluenesulfonyl hydrazide. There are no particular restrictions on the amount used, and it can be selected as appropriate; for example, an amount of about 0.2 to about 15 parts by weight can be exemplified based on 100 parts by weight of the vinyl chloride resin (A). 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, and quaternary ammonium chloride. , quaternary ammonium sulfate, and the like. The amount to be used is not particularly limited and can be selected as appropriate, but for example, it may be about 0.2 to about 10 parts by weight based on 100 parts by weight of the vinyl chloride resin (A). In addition, flame retardants include tributyl phosphate,
Phosphate esters such as diphenyl octyl phosphate, halogen-containing phosphate esters such as tris(2,3-dibromopropyl) phosphate and tris(bromochloropropyl) phosphate, halogen compounds such as chlorinated diphenyl and tetrabromobenzene, Examples include antimony-based flame retardants such as antimony trioxide and triphenylstibine. There are no particular restrictions on the amount used, and they can be selected or used in combination as appropriate.For example, (A) vinyl chloride resin 100
An example may be an amount of about 0 to about 20 parts by weight. Furthermore, other compatible resins include ethylene/
An example is vinyl acetate copolymer. The amount used is, for example, 0 to 35 parts by weight per 100 parts by weight of the vinyl chloride resin (A). The semi-rigid vinyl chloride resin composition of the present invention can be in the form of a molded article molded by any method known per se. For example, it can be in the form of any molded article known in the field of films (including sheets) and other semi-rigid vinyl chloride resin components, but may also be in the form of marking films such as those already mentioned, as well as plastic films, plywood, metal plates, etc. It can be advantageously used as a film for laminating with metal foil, paper, cloth, etc. In particular, it shows outstanding 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), (C), and (D), and further, if desired, other additives such as those exemplified above, may be added as necessary, such as in a ribbon blender, Henschel mixer, pony mill, dispersion machine, etc. Mix using other appropriate mixing means, and if desired, kneading rolls, Banbury mixer,
The mixture can be heated and kneaded using an appropriate kneading means such as an extruder and then subjected to molding. Examples of molding techniques include calendar molding, extrusion molding, injection molding, cast molding, and sol cast molding. In the present invention, as a molding method for optimal marking film use, use of cast molding method and calendar molding method is preferred, and use of cast molding method is particularly preferred. When using the cast molding method, the above-mentioned
Components (A), (B), (C), and (D), an appropriate solvent, and optionally other suitable additives such as those exemplified above are mixed with stirring to prepare a vinyl chloride resin composition in the form of a solution. can be formed. Such a vinyl chloride resin composition can be used without the need to apply special external stress.
It can flow freely by gravity alone and give the desired shape, and the solution in the desired shape is simply heated and dried to form a film, giving the desired cast molded product. The heat drying conditions are, for example, about 30 to about
Examples include conditions such as 200°C for 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, isopropylbenzene, and cyclohexane; methyl acetate, ethyl acetate,
Esters such as butyl acetate, isobutyl acetate, butyl propionate; ethers such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, diethylene glycol monoethyl acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, dioxane; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isopropyl ketone, ethyl n-butyl ketone, isophorone, cyclohexanone; halogenated hydrocarbons such as chloroform, methyl chloroform, epichlorohydrin, trichlene; tetrahydrofuran, tetrahydrofurfuryl alcohol, etc. Examples include furans; 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, an asformed film formed by a calendar molding machine is heated at a temperature of about 30°C or less, for example, from about -10 to about 30°C, using a gaseous refrigerant, such as air, nitrogen, or Preferably, quenching is performed with a gaseous refrigerant such as carbon dioxide. For example, the calender molding temperature is approximately
For example, the temperature may be 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 carried out 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 temperature of each of the cylinder part, adapter part, and die part may be appropriately set between 140 and 220°C depending on the capacity of the processing machine. When trying to obtain a substantially unstretched film with a thickness of about 30 to 100μ, the die lip gap should be set to 0.2μ.
This method is advantageous when producing a relatively thick film of about 100 μm, since it is necessary to set the thickness to be less than m/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 stress: - A tensile test sample was cut from the sample film in accordance with JIS-K-6734, and using this sample, the tensile speed was 200 m in an environment with a temperature of 23 ± 2°C and a relative humidity of 65 ± 5%. A tensile test is performed using a tensile tester under the conditions of /min. 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 calculated as the width (mm) x thickness of the sample before the test. The yield stress is the value (Kg/mm ² ) divided by (mm). (2) Adhesion retention: - Apply 30μ thick acrylic adhesive (product name: Nitssen PE-121, Nippon Carbide Industries Co., Ltd. product) to one side of a 50μ thick sample film, and coat the coated surface with silicone. Laminate the release paper and use it as a sample. This sample
After heat treatment for 336 hours in an oven adjusted to 80±2°C, it is left at room temperature for 24 hours. From the sample after this heat treatment, width 25mm, length
Cut out a 200mm test piece. The release paper of the test piece was removed, and the test piece was adhered to the surface of a SUS304 plate having a No. 180 Emery polishing surface using a 2 kg pressure roll. After pasting, the specimen was left in an environment with a temperature of 23 ± 2°C and a relative humidity of 65 ± 5% for 24 hours, and then the specimen was gripped at one end in the length direction and peeled off at a peeling speed of 300 m/min on the opposite side from the gripped end. Adhesive force a (Kg/cm) measured as the force required to peel off in the end direction (180° direction)
shall be. Adhesion strength b measured in the same manner using the same sample except that the above heat treatment was not performed.
(Kg/cm) and calculate the adhesive strength retention rate according to the following formula. Adhesive strength retention rate (%) = a / b × 100 (3) Printing ink adhesion: - A screen printer ( Product name Minomatuto 600L; Mino Group product)
Then, printing was performed using a 200 mesh monotetron printing screen using printing ink (LOV-710Black; manufactured by Seiko Advances). 50
After drying for 30 minutes in an oven adjusted to ±3℃, 100 crosscuts with a 1mm gap were
Cross Hatch Cutter (Model: 295/I,
ERICHSEN product) and press the Nichiban cello tape to this cross cut part. Peel off the cellophane tape 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. Evaluation Peeling standard number of crosscuts out of 100 crosscuts 10th grade 0 9th grade 1~10 8th grade 11~20 7th grade 21~30 6th grade 31~40 5th grade 41~50 4th grade 51~60 3rd grade 61~70 2nd grade 71~80 Grade 1 91~100 (4) Weather resistance: - Attach the sample to a 1 mm 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 standard condition: 5th grade: There is no dirt on the film surface, and there is no discoloration or fading. 4th grade: There is some dirt on the film surface, but it can be removed by wiping. 3rd grade: There is no discoloration or fading. There is some dirt on the film surface, and it cannot be wiped off. 2nd grade, where slight stains remain even when the film is exposed to dirt. Slight discoloration and fading are visible. Dirt on the film surface is noticeable and some stains remain after wiping. 1st grade, where significant discoloration and fading is observed. Most of them remain as stains. Discoloration and fading are also significant (5) Workability (suitability for adhesion to curved surfaces): - Laminate sample used for adhesive strength retention
Cut to size 100mm. After peeling off the release paper, it is tested by pasting it on a predetermined position at the apex of a hemispherical stainless steel ball with a diameter of 300 mm, and the ease of pasting and the appearance, shape, etc. of the pasted product are evaluated using the following evaluation criteria. Grade 3: Easy to paste, the appearance of the pasted product is good, and no peeling occurs even after 24 hours. Grade 2: Wrinkles and 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 application process, making it difficult to apply it to the adherend in 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. Γ Ethylene/vinyl ester resin A carbon monoxide-vinyl acetate-ethylene copolymer with the composition listed in Table 1. Γ Acrylic resin Methyl methacrylate/butyl acrylate = 85/15 Number average molecular weight (M) 11500 Glass transition temperature Tg (℃) 65 Properties (23℃) Solid. Γ Polyester plasticizer propylene glycol-butanediol,
A polyester plasticizer made of mixed alcohol of hexanediol and adipic acid with a number average molecular weight (M) of approximately 3000. Examples 1 to 4, Reference Examples 1 to 11, and Comparative Examples 1 to 6 Vinyl chloride resin shown in Table 1 below [Nicabinyl SG-1100N, Nippon Cavide Co., Ltd. product, average degree of polymerization of about 1100], polyester Plasticizer ethylene/
In addition to containing vinyl ester resin, acrylic resin and Al paste in the amounts shown in Table 1,
For 100 parts by weight of vinyl chloride resin, 3.0 parts by weight of Ba/Zn stabilizer (AP-539; manufactured by Adeka Argus Chemical Co., Ltd.) 0.5 parts by weight of ester lubricant (Bu-St; manufactured by Kawaken Huain Chemical Co., Ltd.) 2 parts by weight of benzotriazole-based ultraviolet absorber (Tinuvin P; Ciba Geigy product) A film with a thickness of 50 μm was produced from the mixed resin component by a prescribed processing method, and the physical properties of the obtained film were measured by the method described above. The results are listed below in Section 1.
Shown in the table. (i) Casting method Tetrahydrofuran is added so that the resin concentration of the mixed resin component is 20% by weight, and the mixture is poured into a closed container.
A resin solution composition was obtained by stirring and dissolving at 100°C for 2 hours. Next, the resin solution composition was cooled and defoamed, and then cast onto a stainless steel plate using a caster.
Hot air drying was performed at 140° C. for 15 minutes and peeled off to obtain a dried film with a thickness of 50 μm. (ii) Calendar method The mixed resin components are pre-kneaded using a ribbon blender at 100°C for 30 minutes, then melt-kneaded using two rolls at 150°C for 10 minutes, and then mixed with four inverted L-shaped calender rolls. A film with a thickness of about 50μ was obtained at a roll temperature of 175 to 180°C.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) 100 parts by weight of a vinyl chloride resin containing 0 to 20% by weight of a copolymer component, (B) a liquid polyester plasticizer with a number average molecular weight (n) of 1500 or more and 0 to 10 parts by weight of other plasticizers for vinyl chloride resin, (C) In the main chain consisting of ethylene/vinyl ester of saturated carboxylic acid/carbon monoxide copolymer resin, [formula ] Based on the total amount of plasticizer (B) above, the ethylene/vinyl ester resin having a bond is
and (D) a number average molecular weight (n) of 1500 to 50000, and
Contains a low molecular weight acrylic or methacrylic resin that is solid at 23°C, but excluding acrylic or methacrylic graft copolymer resins, in an amount of 5 to 20% by weight based on the above (A) vinyl chloride. 1. A semi-rigid vinyl chloride resin molding composition for marking film, which has a yield stress of 1 to 6 Kg/mm ² . 2 The liquid polyester plasticizer has 4 to 15 carbon atoms.
The semi-rigid vinyl chloride resin molding composition according to claim 1, which is a liquid polyester plasticizer derived from a dibasic acid and a dihydric alcohol having 2 to 20 carbon atoms. 3. The semi-rigid vinyl chloride resin molding composition according to claim 1 or 2, wherein the semi-rigid vinyl chloride resin molding composition further contains an ultraviolet absorber. 4. The semi-rigid vinyl chloride resin molding composition according to claim 1 or 2, which has a yield stress of 1 to 5 Kg/mm ² .