JPS60195146A - Composition for semirigid vinyl chloride resin moldings - Google Patents

Abstract

PURPOSE:A composition that is obtained by adding a specific polyester plasticizer, ethylene/vinyl ester copolymer resin to a vinyl chloride resin in a specific proportion, thus being suitable for forming marking films, because the composition gives moldings with an appropriately high level of toughness. CONSTITUTION:The objective composition is obtained by mixing (A) 100pts.wt. of vinyl chloride resin containing 0-20wt% of a copolymerizing component, with (B) 10-25pts.wt. of liquid polyester plasticizer of more than 1,500 number-average molecular weight, (C) 0-10pts.wt. of other plasticizer for vinyl chloride resin and (D) 5-20pts.wt. of ethylene/vinyl copolymer resin (substantially free from thermoplastic polyurethane resin) so that the yield stress is adjusted to 1-6kg/ mm.<2>. Component B is, e.g., a polyester plasticizer from a dibasic acid of 4-15 carbon atoms such as maleic acid and a dihydric alcohol of 2-20 carbon atoms such as ethylene glycol. EFFECT:Moldings has improved adhesion to pressure-sensitive adhesive, flexibility and printability.

Description

Detailed Description of the Invention This JT is suitable for molding semi-rigid vinyl chloride resin molded products such as films, sheets, overlay films, and laminating films, and is particularly excellent as a marking film molding composition. Semi-hard 'i'l with both properties
A juXed bivinyl resin molding composition.

More specifically, the yield stress is 1 to 6 kV/mn? flexibility with moderate stiffness as shown by , adhesive strength retention of the pressure-sensitive adhesive when a pressure-sensitive adhesive layer is provided on the film of the composition, and printing on the film. Improved properties such as adhesion between printing ink and film, surface smoothness, weather resistance, adhesion to curved surfaces when used as a marking film, and ultraviolet absorber retention properties. The present invention relates to a semi-rigid vinyl chloride resin molding composition.

In particular, the number average molecule 1ri: (Mn) is about 100 parts by weight of vinyl chloride resin containing 0 to about 20% copolymerized component about 10 to about 25 parts by weight of a liquid polyester plasticizer of 1,500 or more, θ to about 10 parts by weight of another plasticizer for vinyl chloride resin, and about 5 to about 5 to about ethylene/vinyl ester copolymer resin (Q) A semi-rigid vinyl chloride resin molding composition comprising a composition containing 20'1jTi jtt part and substantially no thermoplastic urethane resin, and having a yield stress of 1 to 6 kg/mn? To be knowledgeable.

Conventionally, vinyl chloride resins range from soft vinyl chloride resins plasticized with liquid plasticizers to unplasticized hard vinyl chloride resins (
Resins with different degrees of plasticization over the η1 resin are known, and depending on the degree of plasticization, resins exhibit a wide range of physical properties ranging from rubber-like elastic to rigid, and are used in various applications. It is provided. 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, it is normal that the proportion of plasticizer in the composition is relatively large, and troubles caused by or related to plasticizer bleed-out occur. Also, there are problems of deterioration of the physical properties of the vinyl chloride resin, and therefore, proposals have been made to overcome such problems. 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 in the specific range of [F]) may be used in combination with other plasticizers for vinyl chloride resins up to about 1 () M parts per 100 parts by weight of the vinyl chloride resin (4) above. Liquid polyester that satisfies the average molecular weight (Mn) conditions can be used.
It satisfies the bonding parameters of about 10 to about 25 parts by weight of the plasticizer and about 5 to about 20 parts by weight of the ethylene/vinyl ester copolymer resin (C), and has a yield stress of 1 to 6 kg.
/mn? By satisfying the bonding requirements of, flexibility with appropriate stiffness, adhesive strength retention of the pressure-sensitive adhesive when the pressure-sensitive adhesive layer is provided on the film of the composition, It has excellent adhesion between the printing ink and the film when printed on the film, surface smoothness, weather resistance, suitability for adhesion to curved surfaces when used as a marking film, and ultraviolet 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 properties and, in particular, has various excellent properties desired in a marking film molding composition.

For example, motorcycles, four-wheeled vehicles and other types of vehicle widths, land and sea containers, yachts, boats and other types of vessels, vehicles and containers, furniture, door boards, window panels, Striped borders for decoration or display of pillars and other building materials; advertising stickers used to display advertising characters, figures, patterns, etc. on signboards and billboards; traffic signs, road signs, guides Marking films are used in a wide variety of fields, such as boards, danger prevention signs, and stickers for various displays such as product marks F and j'i.

A marking film such as Kono 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. However, in conventional marking films, the plasticizer in the film bleeds into the adhesive layer and loses its adhesive strength over time. There was a problem in that the adhesion to the base material deteriorated. Furthermore, the plasticizer in the film bleeds out to the marking film 4 (column 1) on the opposite side of the adhesive layer, promoting the adhesion of dust in the air and easily contaminating the marking film surface. There is also a problem with poor weather resistance.Also, when printing is applied to the surface of the marking film, conventional marking films have problems in that the adhesion between the printing ink and the film is insufficient and it easily peels off. Furthermore, the suitability for adhesion to curved surfaces was also unsatisfactory.Furthermore, since marking films are often used outdoors, it is common to add UV absorbers; The absorbent easily volatilizes due to heat during film molding, and furthermore, such films 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 10 to about 25 parts by weight of a liquid polyester plasticizer satisfying the number average molecular weight (Mn) condition, and about 5 to about 2 parts by weight of a resin (heated) By satisfying the bonding parameters (substantially containing no plastic urethane) and the bonding requirements of a yield stress of 1 to 6 kg/mJ (L, the above-mentioned difficulties were overcome, and later along with the examples As shown experimentally with many comparative examples, it has been discovered that it is possible to provide a semi-rigid vinyl chloride resin molding composition, in particular a marking film molding resin composition and a molded article, which have excellent improved properties. Ta.

Furthermore, since the composition of the present invention does not substantially contain a thermoplastic urethane resin, it can be conveniently manufactured by a casting method, and has the attendant advantage of good surface smoothness.

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. (T i(F
), the so-called solution casting method in which a film is obtained by dissolving in methyl ethyl ketone (MEK) or the like, casting, and drying;
Molding methods such as sol casting, which obtains a film by hot melting, can be mentioned.

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

■ Used in the semi-rigid vinyl chloride resin molding composition of the present invention
There are no particular restrictions on the vinyl chloride resin, and vinyl chloride resins conventionally used for molding can be appropriately selected and used. 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 2000, more preferably about SOO to about 1 soo, particularly preferably about 1200 to about 1600.

Furthermore, the substituted vinyl resin can also be a resin for vinyl chloride paste.

2. (5) In addition to the vinyl chloride homopolymer, the vinyl chloride resin may contain up to about 20% by weight, preferably about 10 weight tL.
Particularly preferred are copolymers containing up to about 6% by weight of copolymerized components. Examples of such copolymer components are vinyl monomers, 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, ethyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, propyl methacrylate, ethylene glycol dimethacrylate, etc. (meth)
Acrylic acid ester monomer. Vinyl ester monomers such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate, and the like. Vinyl ether monomers such as methyl vinyl ether, flobyl vinyl ether, butyl vinyl ether/L/, phenyl vinyl ether, allyl vinyl ether, and the like. Examples include copolymers of styrene derivatives such as styrene, methylstyrene, dimethylstyrene, vinylstyrene, chlorostyrene, vinylphenol, and the like.

The above-mentioned substituted vinyl resin 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, Nikabi=-#5G
-7005SG-800, 5G-1100, 5G-13
00,5G-1400, [vinyl chloride resin, Ryoichi Co., Ltd. product], Zeon 121, Zeon 131, Zeon 25,
Zeon 135J [vinyl chloride resin, Nippon Zeon Co., Ltd. product], Vinyiki 51MF, Vinica P-440, Vinica P-400 [vinicy chloride 01 resin, Mitsubishi Monzanto Co., Ltd. product], Sumilit PX [vinyl chloride resin, Sumitomo Chemical Examples include commercially available vinyl chloride resins such as the following:

0 used in the semi-rigid vinyl chloride resin molding composition of the present invention
3) The plasticizer is (5) vinyl chloride resin 100 as described above.
The number average molecular weight (Mn) is approximately 1.50 with respect to the M weight part.
0 or more, preferably about 1,500 to about 6,000. More preferably about 1,500 to about 4,000. More preferably about 2,000 to about 4,000 parts by weight of a polyester plasticizer, about 10 to about 25 parts by weight, preferably about 12 to about 20 parts by weight, and O to about 10 parts by weight of other plasticizers for vinyl chloride resins. It is a drug.

Examples of such liquid polyester plasticizers include one to three dibasic acids selected from C1 to CI5 dibasic acids such as maleic acid, adipic acid, phthalic acid, azediic acid, and sebacic acid, and ethylene glycol. Recall, 1.2
-Flopylene glycol, 1,3-butylene glycol, 1,4-butanediol, neopentyl glycol,
Dipropyl glycol, 1,6-hexanediol, 2
, 2.4-trimethyl 1,3-bentanediol, 1.
1 to 5 types selected from C1 to C7o dihydric alcohols such as 5-bentanediol, and a chain stopper appropriately selected from acetic acid, coconut oil fatty acid, n-octyl alcohol, and n-decyl alcohol. 2jt of the liquid polyester plasticizer obtained by this process can be used. The liquid state of the liquid polyester plasticizer of the present invention is defined as a viscous liquid whose viscosity at 25°C is 500,000 voids or less using a BH type rotational viscometer, and the number average molecule M (Mn) of the polyester plasticizer is determined by GP C (Gel Permeat
ion chromatography) method and is a converted value.

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.), MS
-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-i7i, DIDA, 5P-501, 5p-115
8 (polyester plasticizer, Sanken Kako Co., Ltd. product),
Kodaflex NP 10 (Polyester plasticizer, East;man Chemical Prod
ucts product), Flexol R-2,H (polyester plasticizer, Union Carbide Corp.
, Ltd. product), Edenol 1200 (polyester plasticizer, Henlcel product), Rheoplex
100, Rheoplex 110, Rheoplex
220 (polyester plasticizer, C1ba-Ge
Examples include products such as those manufactured by Igy Co., Ltd. Such polyester plasticizers can be used not only in one type but also in combination of two or more types.

In the composition of the present invention, (8) a small amount of other plasticizer for vinyl chloride resin, preferably up to about 10 parts by weight, preferably up to about 5 parts by weight, may be used in combination with 100 parts by weight of the vinyl chloride resin. I can do it. Examples of such other plasticizers for vinyl chloride resins include esters of C1 to C35 monohydric or polyhydric alcohols of -C7 to csi mono- or polybasic carboxylic acids and oxiranes with an oxygen content of 2
~9 molar molecular weight less than about 2,000, e.g. about 10
~about 2. ooo epoxy compounds can 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 7-thalate, diisooctyl phthalate, diisobutyl phthalate, diethyl phthalate, diisodecyl phthalate, ditridecyl phthalate, ditridecyl phthalate, di( heptyl nonyl undecyl) phthalate, benzyl phthalate, butyl benzyl *phthalate, dinonyl phthalate, Φ normal alkyl
phthalate, di-n/isoalkylphthalate, etc. (15 monohydric or polyhydric alcohol esters; e.g., dimethyl isophthalate, di(2-ethylhexyl)-isophthalate, diisolkyl phthalate, etc.) 01-CSa of isophthalic acid such as octyl inphthalate, polyalkylene glycol isophthalate, etc.
monohydric or polyhydric alcohol ester;
-C of tetrahydrophthalic acid such as n-octyltetrahydrophthalate, diisodecyltetrahydrophthalate, c, ~C8° alkyltetrahydrophthalate, etc.!
Monohydric or polyhydric alcohol esters of -Css; for example, adipic acid such as di-n-butyl adipate, di(2-ethylhexyl) adipate, diisodecyl acylate, benzyl octyl adipate, di(butoxy ethoxyethyl) adipate, etc. Monohydric or polyhydric alcohol ester of 01 to CB5; fc t, t
Jf, cy(2-x fhexyl) azelate, diyneoctyl azelate, di-2-ethylhexyl-4
- C1-c3I of azelaic acid such as thioazelate, etc.
+ monohydric or polyhydric alcohol ester; for example,
01-C3, monohydric or polyhydric alcohol esters of sebacic acid such as di-n-butyl sebacate, di(2-ethylhexyl) sebacate, etc.; e.g.
Chimaleic acids such as n-butyl maleate, dimethyl maleate, diethyl maleate, etc.
hydric or polyhydric alcohol esters; e.g.
n-butyl fumarate, di(2-ethylhexyl)
monohydric or polyhydric alcohol ester of CI=Css of fumaric acid such as fumarate; for example, tri(2
mono- or polyhydric alcohol esters of trimellitic acid such as tri-n-octyl trimellitate, tri-n-octyl trimellitate, tri-isodecyl trimellitate, etc.; Is it like triethyl citrate? 7) C1-C
Monohydric or polyhydric alcohol ester of 3a; for example, C1 to itaconic acid such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, etc.
C5, monohydric or polyhydric alcohol ester of oleic acid such as butyl oleate, tetrahydrofuryl oleate, glyceryl monooleate, etc.
1 to C36 monovalent or divalent or polyhydric alcohol ester: For example, CI to C5 monovalent or polyhydric alcohol ester of ricinoleic acid such as methyl acetyl lysyllate, butylacetyl lysyllate, glyceryl monolysyllate, etc. esters of stearic acid, such as i, f, n-butyl stearate, glyceryl monostearate, diethylene glycol distearate, etc.
Monohydric or polyhydric alcohol esters of c, , and others; diethylene glycol monolaurate, benzenesulfone butyramide, trimethyl phosphate, triptoxyethyl phosphate, tetra-2-ethylhexylhyromellitate, diethylene glycol dibenzoate, glycerol・Monoacetate, chlorinated paraffin, oxirane oxygen containing iJ 2-9% molecule j11°
Epoxy derivatives below 1000.

The semi-rigid vinyl chloride resin molding composition of the present invention contains an ethylene/vinyl ester copolymer resin as an essential component, together with the above-mentioned (A) vinyl chloride resin and (B) liquid polyester plasticizer. It contains 20 parts by weight, preferably about 7 to about 15 parts by weight.

The vinyl ester of the (a) ethylene/vinyl ester copolymer resin includes vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl persate, vinyl stearate, etc. Preferred is vinyl acetate.

(0) Ethylene-vinyl acetate copolymer system resin suitable as the ethylene/vinyl ester copolymer resin C (hereinafter sometimes referred to as vinyl acetate 1 VAO) and I, high-pressure bulk polymerization method, solution type method, Resins produced by emulsion polymerization and other methods can also be used; for example, Evaflex P-19'07' (VA, ) manufactured by Mitsui Polychemical Co., Ltd., 19% by weight
), Evaflex 410 (VAO 119% by weight),
P-', '2505 (VAO125fi quantity chi), Evaflex 260 (VAOl 28tt15), P
-3307 (VA, 0130 weight section) Hereditary Vaflex 150 (VAO 133% by weight), Evaflex 4
0LX (VAO140 weight section), E hereditary Rex 45L
X(VAo.

45tR%), diethylene BH (VAO 155% by weight) manufactured by Nippon Gosei Kagaku Kogyo 1), 0HrVAO, 60if
%), Levaprene 450P145ON (V
Ao, 45 heavy i1-section), lutracene manufactured by Toyo Vtac Co., Ltd., ebatate manufactured by Sumima Kagaku Kogyo C Co., Ltd., and Yucalon Epa manufactured by Mitsubishi Yuka Co., Ltd.).

The content of vinyl acetate in the ethylene-vinyl acetate copolymer resin is preferably about 18 to about 50% by weight, preferably about 25 to about 50% by weight, particularly preferably about 30 to about 48% by weight.
A weight scale can be suitably used.

As explained in detail above, the semi-rigid vinyl chloride resin molding composition of the present invention comprises: (4) a vinyl chloride resin 100 type opening containing a polymeric component of 0 to 201 fi%, preferably 0 to about 1 fi%; (B) Number average molecular weight -9 (Mn) is 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 2.00
0 to about 4,000 liquid polyester plasticizer total about 10
~25 parts by weight, preferably about 12 to about 20 parts by weight, and θ to about 10 parts by weight of other vinyl chloride 4b1 plasticizers.
parts, preferably 0 to about 5 parts by weight, and (0) about 5 to about 20 parts by weight of the ethylene/vinyl ester copolymer resin, preferably about 5 to about 15 parts by weight, more preferably 1 part by weight.
The structure contains about 7 to about 15 parts by weight, and has a yield stress of 1 to 6 kp/- preferably 1 to 5 kg/mA.
More preferably, it is 1.2 to 4 kq/-.

The composition of the present invention satisfies the above bonding requirements, thereby providing N degree of back strength. flexibility, 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 syllables on the film, and surface smoothness. It has excellent properties such as weather resistance under outdoor usage conditions, suitability for adhering to curved surfaces when used as a marking film, and ultraviolet absorber retention.

The excellent combination of the above-mentioned properties in the composition of the present invention includes the combination of the above-mentioned (A), (components Bl and (0) mutually influencing and coalescing), the male side, and each of the above-mentioned bonds. Although it is difficult to describe the effect of each parameter in terms of ktA, there will be many comparative examples and examples later. As shown and shown experimentally, deviating from the bonding requirements specified in the present invention,
In practice, it is extremely difficult to achieve all of the above excellent properties in the composition of the present invention.

When the vinyl chloride resin contains all of the copolymerized components, the amount of the copolymerized component is up to about 20% by weight, preferably up to about 10% by weight, and more preferably up to about 61% by weight.

If the copolymerization component exceeds the above range and there is too much bone, for example,
If the amount is less than about 20 μm, it is recommended to use the first
It is better to use 1.

゛Although the degree of polymerization of (A) vinyl chloride resin can be selected as appropriate, as mentioned above, the degree of polymerization is about 600 to about 3000,
Preferably L< is about 700 to about 2000, more preferably about 8
00 to about 1800, preferably about 800 to about 16
(4) Vinyl chloride having a degree of polymerization as exemplified above can be obtained when the polymerization degree is about 00, since more preferable results can be obtained in terms of workability during film production and the various physical properties of the obtained film. The use of resins is advantageous.

The number average molecular bone (Mn) of the polyester plasticizer (R)
) is about 1.500 or more, preferably about 1,500 to about 8
,000, more tf (2gu is about 2.000 to about 6.0
00 range 3,000-5,000, approximately 1.50
If the total bending is too small by more than 0, the tendency of plasticizer bleed out will be disadvantageously increased under the bonding requirements with other requirements of (A) and (0), and the adhesive strength, surface smoothness, weather resistance However, when the liquid polyester plasticizer becomes a solid polyester plasticizer, the elongation rate of the film decreases. and the film becomes undesirably brittle. Therefore, as the liquid polyester plasticizer (B), a polyester plasticizer that fully satisfies the above number average molecular weight (Mn1 condition) is selected and used.

Furthermore, the use of the (B) liquid polyester plasticizer'i1
i' is (about 10 to about 25 to 7 parts per 100 parts of vinyl chloride octopus fat, preferably about 12 to about 20 parts),
4. However, if the amount of the liquid polyester plasticizer (B) used exceeds the above range and is too small, the film will be This is inconvenient because it tends to lose its proper flexibility, and
If the amount exceeds the above range and exceeds the above range, the adhesive strength will deteriorate, and the adhesion between the printing ink and the film, surface smoothness, weather resistance, curved surface adhesion when used as a marking film, etc. will deteriorate. Will UV+M lli retentivity deteriorate? accompany. Therefore, the amount should be selected appropriately within the above range.

Further, the amount of other vinyl chloride resin plasticizers that may be used in combination with the above liquid polyester plasticizer is up to about 10 parts by weight based on 100 parts by weight of (A) the vinyl chloride clear phase. If the amount of other plasticizers exceeds about 1oM and is too excessive, bleed-out will increase, adhesive strength will decrease, and the adhesion between printing ink and film, weather resistance, etc.
This is undesirable in that it causes problems such as the retention of ultraviolet absorbers.

The amount of the ethylene/vinyl ester copolymer resin (C) is about 5 to about 20 parts by weight, preferably about 5 to about 15 parts by weight, and more preferably about 7 to about 15 parts by weight.

If the amount of component (0) used is too small and deviates from the above range, the film will lose appropriate flexibility and become brittle due to the combination of other requirements, making it difficult to use as a marking film. This may cause the inconvenience of poor adhesion to curved surfaces, and if too much is used, the adhesion with printing ink and weather resistance will deteriorate due to the combination of other requirements, and the film will be too flexible, making it difficult to bond with the marking film. 1. Adhesion to curved surfaces tends to deteriorate when used on surfaces.

Therefore, the amount of component (0) to be used should be appropriately selected within the above range.

The semi-rigid vinyl chloride resin molding composition of the present invention meets the above bonding requirements. (A), (Fl) and (0
)? and has a yield stress of 1 to 6 to 9/-, preferably 1 to 5 to 9/-, and more preferably 1.2 to 4 im
Satisfies the requirements of A. Compositions with a yield stress of zero or close to zero, such as those in ordinary soft vinyl chloride resin compositions containing a relatively large amount of liquid plasticizer, have a moderate stiffness required in the present invention. If the yield stress deviates from the above range and is too low, the film will not be as flexible when attached to the intended adherend. Because it stretches, it becomes difficult to paste it in the specified position and with the specified dimensions, which spoils the appearance.Also, if it is too high outside the above range, it will not conform to the curved surface if the adherend is a curved surface. There are wrinkles and it cannot be applied evenly.

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

The semi-rigid vinyl chloride resin molding composition of the present invention may further contain various other additives. Examples of such other additives include colorants, metal powders, and metal powders. Crushed foil, lubricant, stabilizer, antifog agent, ultraviolet absorber,
Examples of the above colorants include titanium oxide,
Zinc white, lead white, charcoal rρ calcium, gypsum, precipitated silica, carbon black, Benga 2, aluminum powder, bronze powder, 4"Q f'J, molybdenum red, cadmium yellow, yellow lead, titanium yellow, chromium oxide green , ultramarine and other inorganic pigments; permanent medium red 4 R no 1 nza e yellow LOG.

Benjishi Yellow GR, Permanent Carmine FB,
Examples include organic pigments such as phthalocyanine blue B and phthalocyanine green.

The amount to be used is not particularly restricted and can be selected as appropriate, but for example, about 0.1 to about 150 parts by weight per 100 parts by weight of the vinyl resin can be exemplified.

Examples of metal powders or crushed metal foils include foil powders or crushed metals of aluminum, brass, stainless steel, lead, iron, etc. There are no particular restrictions on the amount used. For example, the amount may be about 1 to about 50 parts by weight based on 100 parts by weight of (3) vinyl chloride resin.

In addition, examples of the above-mentioned lubricants include vinyl chloride resin layer jlJ
Any known lubricant can be used and can be selected and used as appropriate, but examples include hydrocarbon lubricants such as liquid paraffin and polyethylene wax, fatty acid-based lubricants such as stearic acid and Ogishi fatty acid, fatty acid amide-based lubricants, fatty acids and alcohols. Examples include ester-based lubricants, fatty alcohol-based lubricants, and polyhydric alcohol-based lubricants. The amount used can be selected as appropriate, and for example, the amount used can be about 0.1 to about 10 parts by weight per 100 parts by weight of the vinyl resin. The use of a lubricant can be applied to the composition film of the present invention.
It tends to promote dimensional stability of the film after application to the substrate, often giving favorable results.

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, dioctyltin mercapto stabilizer, dioctyltin mercapto stabilizer, stannane diol derivative and/or stabilizers such as complexes thereof.

The amount used can be selected as appropriate, and for example, an amount of about 10 parts by weight or less per 100 parts by weight of (5) vinyl chloride resin can be exemplified.

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 (g) vinyl chloride resin 1003 (approximately 10 parts by weight or less per part).

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-methoxybenzophenone; 2-Hydroxy-4-n-octogysibenzophenone, 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-
Sulfone benzophenone, 2.2.4.4-tetrahydroxybenzophenone, 2.2-hydroxy-4,4-
Dimethoxy-5-sodium sulfobenzoneenone, 4
-dodecyloxy-2-hydroxybenzophenone, 2
-Hydroxy-5-chlorobenzophenobenzotriazole-2-(2-hydroxy-5-methylphenyl)
Benzotriazole, 2-(2'-hydroxy-57-
methylphenyl)-5-butoxycarbonylbenzotriazole, 2-(2-hydroxy-5-methylphenyl)-5,6-cyclopenzotriazole, 2-(2-
Hydroxy-5-methylphenyl)-5-ethylsulfonebenzotriazole, 2-(2-hydroxy-5'
-tertiary 7'tylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-tertiary methylphenyl)benzotriazole, 2-(2-hydroxy-5-amylphenyl)penztriazole, 2-(2 -Hydroxy-3,5-dimethylphenyl)penztriazole, 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-57carbogysyphenyl)-benzotriazole ethyl ester, 2-(2-methylbenzotriazole/-3'-meth)
5′-iE butylphenyl)penztriazole,
2-(2-hydroxy-3゜5-cy-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methoxyphenyl)benzotriazole, 2-(2-hydroxy-5-phenylphenyl) )-5
-10 ruhensotriazole, 2-(2-hydroxy-5-cyclohexylphenyl)penztriazole/l
/, 2-(2'-hydroxy-5-cyclohexylphenyl)penztriazole, 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)penztriazole, 2-(2-hydroxy-3゜enzotriazole), 2-(2'-hydroxy-5'-phenylphenyl)penztriazole, 2-(2-hydroxy-4-octoxyphenyl) Henctriazole, 2-(2-hydroxy-5-methoxyphenyl)-5-methylbenzotriazole, 2-
(2'-hydroxy-5'-methylphenyl)-5-ethoxycarbonylbenzotriazo-/l/, 2-(2'
-acetoxy-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-cy-tert-butylphenyl)-5-chlorobenztriazole, 2-(2
-human α-xy-3-tert-fA'-5'-methylphenyl)-5-10 lobenzotriazole; ii'ii'' such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate Examples include converted acrylonitrile, hexamethylphosphoric triacetate, etc.
Preferably 2(2-hydroxy-5-methyl-phenyl)benzotriazole, 2(2-hydroxy-3-t-butyl-5
'-Methylphenyl>'-5 Benzotriazole series such as chlorobenzotriazole; Benzophenone series such as 2-hydroxy-4-methoxybenzophenone, 2-human o*cy 4-n-octoxybenzophenone; p-octylphenyl salicylate, phenyl Salicylic acid derivatives such as salicylate; 2-ethylhexyl-2
Examples include substituted acrylonitriles such as -cyano-3,3-diphenyl acrylate, hexamethylphosphoric triamide, and the like. In the present invention, it is a preferred embodiment to use a liquid ultraviolet absorber.

The amount of the ultraviolet absorber to be used can be selected as appropriate, but for example, about 0.00 parts by weight per 10 parts by weight of the vinyl resin.
An example of the amount used is 1 to about 10 parts by weight.

Examples of antioxidants include phenol um forms such as di-t-butyl-p-cresol, amines such as N-phenyl-N'-cyclohexylbara-phenylenediamine, phenyl-alpha-naphthylamine, and their derivatives such as benzimidazole. An example is an anti-rl agent.

The amount to be used can be selected as appropriate; for example, (1) about 0.1 to about 5 parts by weight can be exemplified based on 100 parts by weight of the vinyl chloride resin.

In addition, as blowing agents, azodicarbonamide, azobisisobutyronitrile, N,N'-dini)o7 pentamethylenetetramine, p-)luenesulfonyl hydrazide, p-
Examples include -p-oxybis(benzenesulfonylhydrazide)azobisisobutyronitrile, dinitrosopentamethylenetetramine, and p-toluenesulfonylhydrazide. There is no particular restriction on the amount to be used and it can be selected as appropriate, but for example, (4) about 0.2 to about 15 parts by weight can be exemplified based on 100 parts by weight of vinyl chloride resin. .

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

There are no particular restrictions on the percentage used, and it can be selected as appropriate; for example, (5) an amount of about 0.2 to about 10 heavy parts per 100 weight of vinyl chloride resin can be exemplified.

In addition, as a retardant, halogen-containing phosphate esters such as triptyl phosunate, diphenyl octyl phosphate, etc., esterophoretris (2,3-dibromoglopyl) phosphate, tris (bromochloropropyl) phosphate, etc., and chlorinated diphenyl are used. , halogen compounds such as tetrabromobenzene, antimony-based flame retardants such as antimony dioxide and triphenylstibine, and η. There is no particular restriction on the amount used, and they can be appropriately selected or used in combination. For example, the amount may be about θ to about 20 parts by weight based on 100 parts by weight of (4) vinyl chloride resin.

Further, examples of other compatible resins include ethylene/viniacetate copolymer. The amount used is, for example, (5) 0 to 100 parts of vinyl chloride resin.
An example is an amount of 35 parts by weight.

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 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 advantageously used as a film for laminating plates, metal foils, paper, cloth, etc. Especially with marking film (7
shows outstanding performance.

Molding techniques themselves are known and can be selected and used as appropriate. For example, the essential components (5), If desired, the mixture can be heated and kneaded using a suitable mixing means such as a mixing roll, a Banbury mixer, or an extruder, and then subjected to molding. Examples of molding methods include:
Calendar molding, extrusion molding, injection molding, cast molding,
□Methods such as sol cast molding can be exemplified.O As the molding method for the optimal marking film application in the present invention, use of cast molding method and calendar molding method is preferable, and in particular, cast molding method It is preferable to use

When using the cast molding method, a machined vinyl resin is used and stirred with (B) a plasticizer, (C) an ethylene/vinyl ester resin, an appropriate solvent, and if desired, other appropriate additives such as those exemplified above. They can be mixed to form a vinyl chloride composition in solution. Such a vinyl chloride resin composition can freely flow and form a desired shape by gravity alone without the need to apply any particular external stress, and a solution in the desired shape can be turned into a film simply by heating and drying. As the heat drying conditions that give the desired cast molded product, for example, conditions such as about 30 to about 200°C for about 2 to about 120 minutes can be exemplified. There is no need to use a large-sized molding machine, and the advantage is that there is less heat history on the resin. In the cast molding method, the following solvents are preferably used to dissolve the vinyl chloride composition and further 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, improvylbenzene, and cyclohexane; methyl acetate,
Esters such as ethyl acetate, butyl acetate, isobutyl acetate, butyl propionate; ethers such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, diethylene acetate 1)-col monoethyl ether, ethylcol monobutyl ether, dioxane, etc. Types: Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diimbutyl ketone, isoprobyl ketone, ethyl n-butyl ketone, inholone, cyclohexanone; 7-logenated hydrocarbons such as chloroform, methyl chloroform, evichlorhydrin, trichlene; tetrahydrofuran, Furans such as tetrahydrone rufuryl alcohol; etc. can be mentioned. 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 (asformed film) immediately after molding formed by a calender molding machine is heated at a temperature of about 30° C. or lower, for example, about -
Preferably, the quenching is performed with a gaseous refrigerant at a temperature of 10 to about 30°C, such as air, nitrogen, carbon dioxide, and the like.

The temperature during the stretching is preferably 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.

The machining temperature may be appropriately set between 140 DEG and 220 DEG C. for each of the cylinder part, adapter part, and die part, depending on the capability 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 because it needs to be set 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 resistant surface smoothness and workability (suitability for adhering to curved surfaces, etc.) were measured and evaluated as follows.

fi+ Yield stress test sample was cut out according to pJ Is-6734 from the sample film, and using this Sansol,
A tensile test was conducted using a tensile tester under the conditions of a temperature of 23±2° C., a relative humidity of 65±5, and a tensile speed of 200 ml. The tensile elongation increases as the tensile load increases, but the load (K9) 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 (yx ) X value divided by thickness (K)
g/藺9) is the yield stress.

(2) Adhesive strength retention An acrylic adhesive (
A sample was prepared by applying Niracera PE-121 (trade name: Niracera PE-121, a product of Nippon Car/Tide 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 for 336 hours in an open chamber adjusted to 80±2°C, 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 an 8US304 plate having a No. 180 emery abrasive surface using a two-scent pressure roll.

After pasting, the test piece was left in an environment with a temperature of 23 ± 2°C and a relative humidity of 65 ± 5% for 24 hours, and then gripped at one end in the length direction of the test piece and peeled off the opposite side from the gripped end at a peeling speed of 300 m1-. The force of folding to peel off in the end direction (180° direction) is measured and defined as adhesive force a (Kg/α). Except for the heat treatment described above, the same sample was used and measured in the same manner to determine the fc adhesive force b (Kg/cm 2 ) k, and the adhesive force retention rate was calculated according to the following formula.

Adhesion retention rate (%) -a/b
(Mino Group product), printing ink (LOV-7108
2 using Iack; Seiko AT/Tanzu product)
Printing is carried out using a 00 mesh monotetron printing screen. After drying for 30 minutes in an open chamber adjusted to 50 ± 3°C, 1as + gap cross cut) 100
Cross Hatch Outer (Mod
el: 295/T, ER, 101-1S B
Nitetan sellotape is pressed onto this cross-cut part.

Peel off the Sellotape vigorously, observe with the naked eye the peeling state of the printing ink from the film surface, and check the crosscut 100.
Calculate the number of peeled crosscuts in the middle and evaluate them according to the following evaluation criteria.

Evaluation criteria Number of peeled crosscuts in 100 pieces 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 81-100 (4) Weather resistance A sample was pasted on an aluminum plate with a knee thickness of 1 wx, and exposed outdoors at 45 degrees south. After one year of outdoor exposure, the surface condition of the film was observed.

Evaluation criteria Condition: No discoloration or fading.No discoloration or fading.Slight discoloration or fading.Significant discoloration or fading.Significant discoloration or fading remains.(5)Workability (ability to adhere to curved surfaces)Knee contact force retention The laminate sample used is 5° x 100
Cut to +u+ size. After peeling off the release paper, the adhesive was tested at a predetermined position on the apex of a hemispherical stainless steel gel with a diameter of 300mm, and the ease of application and the appearance and shape of the product were evaluated based on the following evaluation criteria. I'll give it a good evaluation.

Grade 3: The sticker is easy to apply, the appearance and shape of the product with the sticker are good, and it does not peel off even after 24 hours.

Grade 2: Wrinkles or tears occur in the film during the pasting process, or the film does not blend well with the adherend and peels off.

1st grade JIl! During the application process, the film stretches and is difficult to apply to the adherend in place.

(6) Surface smoothness The surface appearance and gloss uniformity of the produced film are visually evaluated according to the following evaluation criteria. Grade 3: Good appearance and gloss uniformity. Grade 2: Gloss is not uniform and uneven. appear.

Grade 1: Noticeable unevenness on the surface.

Additionally, the following ethylene/vinyl ester resins, polyester plasticizers, and vinyl chloride resins were used in Examples and Comparative Examples.

O ethylene/vinyl ester resin-carbon oxide-pynylacetate-ethylene copolymer with the composition listed in Table 1 Acrylic resin methyl methacrylate/butyl acrylate) = 85/
15 Number average molecular weight (Mn) 61,500 Glass transition mixture TtC°C) 65 Properties (23°C) Solid O polyester plasticizer A polyester plasticizer consisting of wet alcohols of propylene glycol, sothanesiols, and hexanediol and adipic acid. The average molecule i (Mn) is about 3000.

0 Vinyl chloride resin 5G-1100N Made by Nippon Card Industry ■ Vinyl chloride: 100, i approx.: 110051ME Mitsubishi Monsanto ■ Split vinyl chloride/vinyl acetate - approx.: 9515% i approx. = 100
0 Examples 1 to 10 and Comparative Examples 1 to 8 Vinyl chloride resin [dicavivinyl 5G-
1100N, Nippon Carbide ■ product, average degree of polymerization approximately 1
100], polyester plasticizer ethylene/vinyl ester resin, acrylic resin and Al paste in the amounts shown in Table 1, and B a / Z n based on 100 parts by weight of vinyl chloride resin. Stabilizer (AP-5
39; 3.0 parts by weight Adeka Argus Chemical Co., Ltd. product) Ester-based lubricant (Bu7St; Yoken 0.5 parts by weight Fine Chemical Company product) Benzo) IJ azole-based external radiation absorber 2 parts by weight (
A film with a thickness of 50 μm was produced using the mixed resin component and a prescribed processing method, and the physical properties of the obtained film were measured using the method described above, and the results are listed below. (1) Casting method shown in Table 1 Tetrahydrofuran was added so that the resin concentration of the mixed resin component was 20%, and the mixture was stirred and dissolved in a closed container at 100°C for 2 hours to obtain a resin solution composition.

Next, the resin solution composition was cooled and defoamed, then 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) Calendar method The mixed resin components were heated to 100% by using a ribbon blender.
Mix 30 molecules at ℃, then mix using two rolls for 15
The mixture was melted and kneaded at 0°C for 10 minutes, using four inverted calender rolls at a roll temperature of 175-180°C to obtain a film with a thickness of about 50μ.

patent applicant Nippon Card Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. (G) Based on 100N parts of vinyl chloride resin containing O to about 20% by weight of a copolymer component, (J3) has a number average molecular weight (diameter) of about 1,500 or more. about 10 to about 25 parts by weight of a liquid polyester plasticizer, 0 to about 10 parts by weight of other vinyl chloride resin plasticizers, and about 5 to about 2 parts of an ethylene/vinyl ester copolymer resin.
0 parts by weight, is made of a composition that does not substantially contain thermoplastic urethane resin, and has a yield stress of 1 to 6 kg/rnrr?
A semi-rigid vinyl chloride resin molding composition characterized by: 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. 3. Claim 1 or 2, wherein 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. The semi-rigid vinyl chloride resin molding composition described above. 4. 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. 5. Is the yield stress 1.2-6 kg/mtr? A composition for semi-rigid vinyl chloride arbor molding according to claim 1 or 2. Margin below