JPS6411751B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a matte wall covering sheet obtained using a resin composition containing a partially crosslinked vinyl chloride resin, and particularly to a matte wall covering sheet with excellent weather resistance. More specifically, a partially crosslinked vinyl chloride resin alone or chlorinated vinyl chloride resin obtained by copolymerizing vinyl chloride or a monomer mixture A containing vinyl chloride as a main component and a monomer mixture B consisting of a bisphenol-modified diacrylate or a bisphenol-modified dimethacrylate. It is a mixed resin with vinyl resin, and the proportion of gel in the total resin component is
The present invention relates to a matte wall covering sheet with excellent weather resistance formed by molding a resin composition having a content of 1.0 to 35% (by weight, hereinafter the same). In recent years, so-called matte molded products that have lost the plastic luster have become popular in vinyl chloride resin molded products in various fields.In particular, with the popularization of fashion, decorative properties are required for wall covering sheets, and various types of Matting techniques have been developed. Among these, matte technology that uses partially crosslinked vinyl chloride resin is attracting particular attention. In other words, matte technology using partially cross-linked vinyl chloride resin has the following advantages: (1) it does not drastically reduce mechanical properties unlike matte technology that uses large amounts of fillers; This is because it has the following advantages: (3) It does not involve an increase in cost, unlike the matting technique, and (3) it does not require special equipment, unlike the matting technique using embossing. Accordingly, compositions containing various partially crosslinked vinyl chloride resins have recently been studied. For example, a proposal was made to obtain a partially crosslinked vinyl chloride resin using a crosslinking agent such as diallyl phthalate, diallyl maleate, polyethylene glycol diacrylate, or polyethylene dimethacrylate, and to utilize a composition using the same (Japanese Patent Application Laid-open No. 54-1989-1). Specification No. 80354,
JP-A No. 56-5843, JP-A No. 54-152054
(specification of Japanese Patent Application Publication No. 56-92024, etc.). However, the use of these partially cross-linked vinyl chloride resins has the disadvantage that the weather resistance of the molded products deteriorates significantly, so if a wall covering sheet that requires weather resistance is to be manufactured, a large amount of ultraviolet absorption is required. It is necessary to use additives, heat stabilizers, anti-aging agents, etc., resulting in high costs. In addition, when used as wall covering materials, the sheets are often painted, which requires the paint to have good adhesion (printability), but conventional products are somewhat unsatisfactory. . In view of the above-mentioned circumstances, the present inventors have conducted intensive research to apply partially cross-linked vinyl chloride resin to the production of sheets for wall covering materials. A partially crosslinked vinyl chloride resin alone or a mixed resin with a vinyl chloride resin obtained by copolymerizing monomer mixture B consisting of bisphenol-modified diacrylate or bisphenol-modified dimethacrylate, which has a gel content in the total resin component. It was discovered that a matte wall covering sheet formed by molding a resin composition having a proportion of 1.0 to 35% has significantly improved weather resistance, and the present invention was completed. Hereinafter, in the present invention, the value obtained by extracting with tetrahydrofuran for 22 hours using a Soxhlet extractor and calculating the dry weight of the extraction residue remaining on a 350 mesh filter will be referred to as the gel fraction. In this specification, the wall covering sheet refers to a sheet that can be used for building, general houses, etc. by pasting it with glass wool, wood, metal, plastic, etc., or by coating the sheet with adhesive and using it as wallpaper. It is applied for interior use. In the present invention, a monomer mixture A consisting of vinyl chloride or vinyl chloride as a main component and a monomer mixture B consisting of a bisphenol-modified diacrylate or a bisphenol-modified dimethacrylate is used.
It is preferable to use a partially crosslinked vinyl chloride resin having a gel fraction of 1.0 to 35% obtained by copolymerizing. Alternatively, a mixed resin mixed with vinyl chloride resin may be used so that the gel fraction is 1.0 to 35%. Monomer mixture A as used herein means vinyl chloride or a mixture of monomers containing vinyl chloride as a main component, and monomer mixture B means monomer mixture A containing bisphenol-modified diacrylate or bisphenol as a crosslinking agent. It means a mixture of monomers mixed with modified dimethacrylate. In the present invention, the bisphenol-modified diacrylate or bisphenol-modified dimethacrylate as the crosslinking agent has the general formula (): General formula (): or general formula (): (In the formula, R ₁ is an H atom or a -CH ₃ group, R ₂ is an H atom or an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ are an H atom, -CH ₃ group, -CH ₂ CH ₃ group) ,−
Atoms or groups selected from CH ₂ CH ₂ COOH groups,
i and j are integers from 1 to 5, m and n are integers from 1 to 10,
1 is 0 or an integer of 1 to 20, and X is a Cl atom, a Br atom, or a hydrogen atom) is preferably used. The amount to be copolymerized with monomer mixture A is 0.35 to 8 parts by weight of the above crosslinking agent per 100 parts by weight of monomer mixture A.
Parts by weight are preferred. Regarding the production of partially crosslinked vinyl chloride resin used in the present invention, patent application No. 56-
It is disclosed in the specification of No. 82862, etc. In the present invention, partially cross-linked vinyl chloride resin can be used alone, but usually polyvinyl chloride resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin,
Vinyl chloride-vinyl acetate copolymer resin, copolymer resin of vinyl chloride and acrylic acid or its derivatives, etc. are blended so that the gel fraction in the total resin component is 1.0 to 35%, and heat is applied as necessary. Stabilizers, lubricants, antioxidants, rubbers, ultraviolet absorbers, processing aids, pigments, plasticizers, etc. are blended and molded to produce hard, semi-hard, or soft matte wall covering sheets. . In the present invention, the gel fraction in the total resin component is 35
If it exceeds 1.0%, the weather resistance will be insufficient;
If it is less than that, the matting effect will not be noticeable and both are unfavorable. As the heat stabilizer added when manufacturing the matte wall covering sheet of the present invention, known heat stabilizers used for vinyl chloride resin can be used, such as tin-based heat stabilizers such as octyltin maleate. Stabilizers, lead-based stabilizers such as tribasic lead sulfate, metal soaps, Ca-Zn-based stabilizers, Ba-based stabilizers, etc. may be used alone or in combination. Further, as the lubricant, known lubricants such as polyethylene wax-based lubricants, stearic acid-based lubricants, and alcohol-based lubricants may be used alone or in combination. Further, thermoplastic resins that can be used in combination include acrylic rubber and EVA. Further, the plasticizers used for softening include known plasticizers such as phthalic acid plasticizers such as dioctyl phthalate, polyester plasticizers, phosphate ester plasticizers, and epoxy plasticizers, alone or Can be used in combination. Further, as the molding method used for producing the matte wall covering sheet of the present invention, common methods such as calendar molding and extrusion molding can be used. Moreover, the molding conditions can be the same as those for ordinary vinyl chloride resin. The matte wall covering sheet of the present invention can prevent the phenomenon of glossing (returning gloss) when bonded with other materials by heat and pressure, and since the surface has irregularities, it also has poor printability and paintability. It is excellent. In particular, durability and heat resistance are significantly superior when using materials other than the partially crosslinked vinyl chloride resin used in the present invention. Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples. Reference Examples 1 to 3 In a stainless steel polymerization vessel with an internal volume of 50, 200 parts of ion-exchanged water (parts by weight, the same applies hereinafter), 0.2 parts of partially saponified polyvinyl acetate, and diisopropyl peroxide.
After degassing, 0.06 parts of lauroyl peroxide, 0.06 parts of lauroyl peroxide, and 0.5 parts each of bisphenol-modified diacrylate shown in Table 1 were added, and after degassing, 100 parts of vinyl chloride monomer was added, and polymerization was carried out at a polymerization temperature of 65° C. for 15 hours. The resulting slurry was dehydrated,
It was dried in a hot air dryer at 55°C for 24 hours to obtain a white powder. The resulting powders were designated as partially crosslinked vinyl chloride resins (1) to (3), respectively, and their gel fractions are shown in Table 1. Reference Examples 4 to 8 In the same manner as Reference Examples 1 to 3, 1.0 part each of ion-exchanged water, partially saponified polyvinyl acetate, diisopropyl peroxide, lauroyl peroxide, and the crosslinking agent shown in Table 1 were added, and after degassing, vinyl chloride was prepared. Monomers were charged and polymerized for 15 hours at a polymerization temperature of 65°C, and white powders were obtained in the same manner as in Reference Examples 1 to 3, respectively. The resulting powders were designated as partially crosslinked vinyl chloride resins (4) to (8), respectively, and their gel fractions are shown in Table 1. Reference Examples 9 to 10 Partially crosslinked vinyl chloride resin (9) was prepared in exactly the same manner as Reference Examples 1 to 3, except that the crosslinking agent used in the production of partially crosslinked vinyl chloride resin (2) was changed to 8 parts. Partially crosslinked vinyl chloride resins (10) were obtained in exactly the same manner as in Reference Examples 1 to 3, except that the amount of the agent was changed to 0.3 parts. The gel fractions were 38% and 0.8%, respectively. Examples 1 to 8 Partially crosslinked vinyl chloride resins (1) to (3) and (9) were blended in a super mixer at 130°C for 5 minutes based on the formulation shown in Table 2, and the resulting compound was The mixture was kneaded for 15 minutes using a mixing roll controlled at 165°C, and the resulting sheet was gradually introduced into an inverted L-shaped calender to obtain a calendered sheet with a thickness of 0.3 mm. Various properties of the obtained calendar sheet were measured and evaluated by the methods shown below. The results are shown in Table 2, and it can be seen that the sheet of the present invention has excellent matting properties and significantly improved weather resistance. Matting property: As shown in the above example, the surface condition of a 0.3 mm thick sheet obtained by calendar molding was visually observed, and the results were rated as ◎Extremely Good, 〇Good, △Slightly Glossy, and ×Glossy. It was evaluated in stages. Weather resistance: The same sheet as above was deteriorated for 200 hours using a sunshine weather meter, and then the elongation rate was measured. In addition, the measurement of elongation rate is based on JIS K
-6724. In addition, the sunshine condition is 63℃ and rain every 2 hours at 18℃.
The test sample was turned over every 20 hours. Printability: Shachihata Kogyo Co., Ltd. on the same sheet as above.
Print on a stamp (5cm x 5cm) with indestructible ink (for plastic) made by the company, dry it at 50℃ for 1 hour, apply adhesive tape to the printed surface, and then remove the tape to remove the remaining ink. Visually observe the remaining area, ◎Remaining area 3/4
Above, 〇Remaining area 3/4~1/2, △Remaining area 1/2~
It was classified into four levels: 1/4 and x remaining area 1/4 or less. Comparative Examples 1 to 8 Using partially crosslinked vinyl chloride resins (4) to (10), the second
Calendar sheets with a thickness of 0.3 mm were obtained in the same manner as in Examples 1 to 8 based on the formulation shown in the table. Various properties of the obtained calender sheets were measured and evaluated in the same manner as in Examples 1 to 8. The results are shown in Table 2, and it can be seen that when the sheets obtained in Comparative Examples 1 to 8 had good matting properties, they had poor weather resistance, and conversely, when they had good weather resistance, they had poor matting properties. Furthermore, it can be seen that the sheets of the present invention are generally better in terms of printability. In addition, Kanevinyl S-1001 and Kaneace PA-20 in Table 2 are each trade names manufactured by Kanebuchi Chemical Industry Co., Ltd., and the gel fraction in the total resin component is the gel fraction of the partially crosslinked vinyl chloride resin. This is a value calculated based on the ratio.

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Claims (1)

[Scope of Claims] 1. A partially crosslinked vinyl chloride resin obtained by copolymerizing vinyl chloride or a monomer mixture A containing vinyl chloride as a main component and a monomer mixture B consisting of a bisphenol-modified diacrylate or a bisphenol-modified dimethacrylate. A matte wall covering sheet with excellent weather resistance formed by molding a resin composition that is a resin composition alone or mixed with a vinyl chloride resin and has a gel content of 1.0 to 35% by weight in the total resin component. . 2 Bisphenol-modified diacrylate or bisphenol-modified dimethacrylate has the general formula (): (In the formula, R ₁ is an H atom or a -CH ₃ group, R ₂ is a H atom or an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ are an H atom, -CH ₃ group, -CH ₂ CH ₃ group) ,−
Atoms or groups selected from CH ₂ CH ₂ COOH groups,
The matte wall covering sheet according to claim 1, which is a compound represented by the following formula: m and n are integers of 1 to 10, and X is a Br atom, a Cl atom, or a H atom. 3 Bisphenol-modified diacrylate or bisphenol-modified dimethacrylate has the general formula (): (In the formula, R ₁ , R ₃ , R ₄ , and X are the same as above, l is 0
or an integer from 1 to 20) The matte wall covering sheet according to claim 1, which is a compound represented by the following formula. 4 Bisphenol-modified diacrylate or bisphenol-modified dimethacrylate has the general formula (): (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , l, and X are the same as above, and i and j are integers of 1 to 5.) Matte wall covering sheet.