JPH0639149B2 - Laminate having vinyl chloride resin sheet with excellent heat resistance as the surface layer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate having a crosslinkable vinyl chloride resin sheet as a surface layer, and particularly to a laminate requiring heat resistance and abrasion resistance. It is about.

"Conventional Technology and Problems" Conventionally, a large amount of flooring and wall coverings having a vinyl chloride resin composition as a surface layer are used, but these contain a considerable amount of plasticizer. Therefore, there is a drawback that the heat distortion resistance and the wear resistance are essentially inferior. In particular, regarding tobacco resistance, the fire of the cigarette butts accidentally dropped melts the surface of the flooring material and creates uneven marks, or the surface swells, lowering the decorative value. It has been desired to improve heat resistance against short-time contact.

As a method for improving such a defect, a method of laminating a soft vinyl chloride resin composition containing a reactive plasticizer on the surface (JP-A-51-88582), a soft vinyl chloride resin composition containing a crosslinking agent (Japanese Patent Laid-Open No. 52-19783), a method of laminating a soft vinyl chloride resin composition using a vinyl chloride resin containing a gel component insoluble in tetrahydrofuran (Japanese Patent Laid-Open No. 55-21217), and the like. Proposed. However, the method using a reactive plasticizer is a method of increasing the hardness of the product by polymerizing the reactive plasticizer during molding, but the method described in the patent is sufficient to modify the vinyl chloride composition. In addition, a significant improvement in heat resistance to high-temperature heating elements such as cigarette fire cannot be expected. Further, in the method of crosslinking using a dithioltriazine-based compound, the heat resistance is excellent, but the thermal stability and weather resistance are poor, and there is an odor.
Hot water whitening is likely to occur. In addition to problems such as poor transparency due to the combined use of cross-linking aids such as MgO, it is difficult to control the cross-linking speed and degree of cross-linking, and there are problems such as relatively long molding time for cross-linking. There is. Further, in the method using a vinyl chloride resin containing a gel component insoluble in tetrahydrofuran, the composition other than the vinyl chloride resin is not crosslinked even though the vinyl chloride resin is partially crosslinked, Essentially, it is not different from a general soft vinyl chloride resin composition and its heat resistance is insufficient.

“Means for Solving Problems” In view of such circumstances, the present inventors have earnestly studied to solve the above-mentioned problems, and as a result, a composition containing a siloxane condensation catalyst was melt-kneaded with a Banbury mixer or the like. ,
Crosslinking occurs during kneading with a mixing roll, etc., and can be easily molded into a sheet by a method such as a calender or an extruder.Also, a composition containing no so-called siloxane condensation catalyst is gradually crosslinked after being molded into a sheet. Has succeeded in providing a laminate having a surface layer excellent in heat resistance suitable as a surface layer of the laminate, and completed the present invention.

That is, the present invention is a laminate having excellent heat resistance, which comprises a resin composition sheet comprising the following components (a), (b) and (c) in the surface layer: (a) vinyl chloride Resin 100 parts by weight, (b) Obtained by hydrosilylation reaction of vinyl resin having carbon-carbon double bond and hydrosilane, or radical copolymerization of vinyl compound and radically polymerizable silane compound having double bond The following general formula (In the formula, R is hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms selected from alkyl, aryl and aralkyl groups, X
Is a hydrolyzable group, and n is an integer of 1 to 3) and is a vinyl polymer having at least one silyl group in the molecule.
3 to 150 parts by weight, (c) plasticizer 30 to 200 parts by weight.

In the present invention, a resin composition suitable as the surface layer of the laminate is a vinyl chloride resin containing a plasticizer, and if necessary, a normal vinyl chloride such as a stabilizer, a lubricant, an ultraviolet absorber, a pigment and a processing aid. It is composed of a system containing an additive used in a resin composition containing a specific vinyl polymer having at least one silyl group in the molecule. This crosslinkable soft vinyl chloride composition is a siloxane condensation product. If it is a composition to which a catalyst is added, surprisingly, a Banbury mixer,
Cross-linking occurs by melt-kneading with a mixing roll, etc., and can be easily taken out in a sheet form by a method such as a calender or an extruder. Also, a composition to which a so-called siloxane condensation catalyst is not added is formed into a sheet form. After that, the crosslinking is gradually promoted, and by using the sheet as the surface of the laminate, a laminate having excellent heat resistance and abrasion resistance is provided. In the present invention, the degree of cross-linking can be easily controlled by the addition amount of the vinyl polymer containing a silyl group. The laminate having the cross-linked sheet as the surface layer has particularly excellent heat resistance and abrasion resistance. It has excellent characteristics.

The vinyl chloride polymer used in the present invention is a vinyl chloride resin obtained by homopolymerizing a vinyl chloride monomer, or a vinyl chloride copolymer resin containing vinyl chloride as a main component, that is, containing 85% or more. Examples thereof include vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin, copolymer resin of vinyl chloride and acrylic acid or its ester, vinyl chloride and methacrylic acid or Examples thereof include copolymer resins with the ester and copolymer resins with vinyl chloride and alkyl vinyl ether. These vinyl chloride copolymer resins may be used by blending in a poor position (up to 30%) with respect to the vinyl chloride resin.

These vinyl chloride resins and copolymer resins thereof can be produced by suspension polymerization, bulk polymerization or emulsion polymerization, and any commercially available vinyl chloride resin can be used.

The average degree of polymerization of the vinyl chloride resin is preferably 700 to 4,500, and when the average degree of polymerization is less than 700, the melt viscosity is reduced and it becomes difficult to perform calendaring and extrusion molding processing,
When the average degree of polymerization exceeds 4,500, melt gelation becomes slow,
The melt viscosity increases, making it difficult to perform calendaring and extrusion molding. The average degree of polymerization is 1,00 for ease of molding.
0-3,500 is preferable.

As the vinyl chloride resin, it is also possible to use a partially crosslinked vinyl chloride resin having a gel component insoluble in tetrahydrofuran as disclosed in JP-A-56-81325 and JP-A-57-195711. it can.

The silyl group-containing vinyl polymer used in the present invention is disclosed in JP-A-54-3.
6395, JP-A-56-43364, JP-A-58-157810 and the like refer to a vinyl polymer having at least one silyl group in the molecule, and the silyl group-containing vinyl polymer is Can be made by the methods of (A) and (B) (A) (In the formula, R is an alkyl group having 1 to 10 carbon atoms, an aryl group,
A monovalent hydrocarbon group selected from aralkyl groups, X is a hydrolyzable group selected from halogen, alkoxy, acyloxy, thioalkoxy, phenoxy, aminoxy and amino groups, and n is a hydroxy compound represented by 1). Can be prepared by reacting a vinyl resin having a carbon-carbon double bond with a group VIII transition metal catalyst. The silyl group-containing vinyl polymer obtained by using halogenated silanes can be used by converting the halogen functional group into another hydrolyzable functional group such as an alkoxy, acyloxy or thioalkoxy group.

The vinyl-based resin is not particularly limited, and a methacrylic acid ester such as methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate, methyl acrylate,
Acrylic esters such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, aromatic vinyl monomers such as styrene and α-methylstyrene, unsaturated nitriles such as acrylonitrile, vinyl acetate, Vinyl esters such as vinyl propionate, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, amide groups such as acrylamide and N-methylol acrylamide, carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride and fumaric acid, A composition that does not significantly reduce the compatibility with one or more vinyl chloride-based resins from vinyl-based compounds such as vinyl chloride and ethylene can be appropriately selected and used. At the time of producing a homopolymer or a copolymer of these vinyl compounds, allyl acrylate, allyl methacrylate, diallyl phthalate, etc. are partially added and radically copolymerized, whereby the hydrosilylation reaction in the vinyl resin is performed. It becomes possible to introduce a carbon-carbon double bond, and the reaction with the hydrosilane compound is selected from platinum, rhodium, cobalt, palladium, nickel and the like.
This can be carried out by using a Group VIII transition metal complex compound as a catalyst, and a silyl group-containing vinyl polymer can be prepared.

(B) As another method for producing a silyl group-containing vinyl polymer, (In the formula, R ₁ is an alkyl group having 1 to 10 carbon atoms, an aryl group,
A monovalent hydrocarbon group selected from aralkyl groups, R ₂ is an organic residue having a polymerizable double bond, X is a group selected from halogen, alkoxy, acyloxy, thioalkoxy, phenoxy, aminoxy and amino groups, and n is It is an integer from 1 to 3. ) Can be produced by radical polymerization of a silane compound represented by The silane compound is disclosed in JP-A-58-157810. Compounds such as are used as vinyl compounds (A)
Other than those described in the method, vinyl compounds having a hydroxyl group such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate can also be used. These vinyl-based compounds may be used alone or in combination of two or more so as not to significantly reduce the compatibility with the vinyl chloride-based resin.

At least one silyl group may be present in the molecule, and the molecular weight of the silyl group-containing vinyl polymer is not particularly limited.
It can be used in the range of 0 to 300,000. 3 vinyl polymer containing silyl group per 100 parts by weight of vinyl chloride resin
~ 150 parts by weight can be added. If the amount of the polymer is less than 3 parts by weight, it can be crosslinked, but the gel content is small, and the heat resistance and abrasion resistance are insufficient when used as the material of the surface layer of the laminate, while the amount of the polymer is 150 parts by weight. If it exceeds, the sheet after cross-linking becomes hard, it is difficult to process, the cost increases, and it becomes impractical as a material for the surface layer of the laminate.

In the present invention, the plasticizer is used to moderately soften the surface layer of the laminate, and the amount of the plasticizer added varies depending on the softness requirement of the surface layer and cannot be specified unconditionally. It is used in the range of 30 to 200 parts by weight in applications such as wall coverings. The hardness of the material of the surface layer can be adjusted to some extent by the composition and the amount of addition of the silyl group-containing vinyl polymer. Examples of the plasticizer include dioctyl phthalate, dinonyl phthalate, phthalic acid plasticizers such as diisodecyl phthalate, dioctyl adipate, fatty acid plasticizers such as dioctyl azelate, trimellitic acid plasticizers such as trioctyl trimellitate, Polyester plasticizers, epoxy compounds such as epoxidized soybean oil, phosphoric acid plasticizers such as tricresyl phosphate, chlorinated paraffins and other plasticizers commonly used for soft vinyl chloride resin structures can be used. .

To crosslink a vinyl chloride resin composition containing a silyl group-containing vinyl polymer, after hydrolyzable groups such as alkoxy groups directly bonded to Si atoms in the polymer are silanolized by contact with water, Further, any compound having a function of promoting dehydration condensation of two silanol molecules to form a Si—O—Si bond to cause crosslinking can be suitably used. The silanol condensation catalysts used in the present invention are known to be a variety of effective substances, and organometallic compounds such as metal salts of carboxylic acids, titanium chelates, alkyl titanate esters, alkyl zirconate esters, organic bases and Includes organic acids. Specific examples of such catalysts are:
Dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin diacetate, stannous octoate, stannous oleate, dibutyltin phthalate, lead octoate,
Zinc 2-ethylhexonate, cobalt naphthenate, cobalt octanoate, iron 2-ethylhexonate, bis (acetylacetonyl) di-isopropyl titanate, di-
Isopropoxy titanium di (ethyl acetoacetate),
Tetrabutyl titanate, tetrabutyl zirconate,
Examples include ethylamine, hexylamine, laurylamine, dibutylamine, piperidine, octodecylamine acetate, p-toluenesulfonic acid and acetic acid. Preferred catalysts are organometallic compounds, in particular tin carboxylates,
For example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate, and dibutyltin phthalate are preferable. The silanol condensation catalyst is 0.01 to 5
It can be used in an amount of parts by weight. The catalyst which is also used as the heat stabilizer for the vinyl chloride resin such as dibutyltin dilaurate may be added with no heat stabilizer. From the aspects of thermal stability and kneading processability of the composition, lead-based heat stabilizers such as tribasic lead sulfate, Ba / Zn-based heat stabilizers Ca-Zn-based heat stabilizers, Cd
-A heat stabilizer such as Ba-based heat stabilizer, zinc stearate, and calcium stearate generally used for processing vinyl chloride-based resin compositions may be used in combination. Stabilizers that do not interfere with transparency are suitable and are generally used in amounts of 6 parts by weight or less. Further, even if a so-called silanol condensation catalyst is not added, crosslinking after the molding process gradually progresses, and heat resistance can be improved.

The resin composition used in the present invention may be mixed with a lubricant, a processing aid, a pigment, etc., if necessary, and the type and amount thereof may be appropriately selected according to the purpose. As examples of the lubricant, those which do not significantly reduce the transparency such as higher alcohols, higher fatty acids and higher fatty acid esters are preferable, and those which are usually used in vinyl chloride-based compositions are used. The seeds are used in an amount of 2 parts by weight or less. Examples of processing aids include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, homopolymers of acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, or copolymers of these esters. Etc. can be used, and generally, it can be used in an amount of 15 parts by weight or less.

The vinyl chloride-based resin sheet having excellent heat resistance used in the present invention can be manufactured by the same manufacturing process as that of a normal vinyl chloride-based resin sheet. A vinyl chloride resin sheet having excellent heat resistance can be formed into a sheet by the same process as that for a normal vinyl chloride resin composition. That is, a vinyl chloride resin, a plasticizer, a catalyst that promotes siloxane bond, a heat stabilizer, a lubricant, etc. are mixed with a stirring mixer such as a ribbon blender, and the silyl group-containing vinyl polymer is added and mixed immediately. The mixture is kneaded with a Banbury mixer, a mixing roll, etc., and calendered into a sheet. Siloxane bonding occurs during Banbury mixer, roll kneading, but the crosslinked composition is surprisingly easy to calender and can be removed as a sheet.

The kneading temperature of the Banbury mixer is preferably 120 to 200 ° C., the degree of polymerization of the vinyl chloride resin in the crosslinkable vinyl chloride resin composition, the type and amount of the plasticizer, and the type of the silyl group-containing vinyl polymer. The optimum temperature is selected depending on the amount. The kneading time may be the minimum time for the composition to gel, and usually 2 minutes or more is sufficient.

The silyl group-containing vinyl polymer and the catalyst for promoting the siloxane bond are preferably separated until just before melt-kneading, and either one of the components is added to the composition immediately before kneading, or by a Banbury mixer or the like. Although one component can be added at the time of melt-kneading, it is preferable to add the silyl group-containing vinyl polymer afterwards.

The laminate of the present invention having a vinyl chloride resin sheet as a surface layer and having excellent heat resistance is a laminate of two or more layers selected from ordinary vinyl chloride resin sheet, asbestos woven fabric, non-woven fabric, paper and the like. It is manufactured by laminating on the surface of. The lamination can be performed by a known method, for example, thermocompression bonding or using an adhesive.

Further, the crosslinkable composition is melt-kneaded in a Banbury mixer and formed into a sheet by a roll, or pellets produced by a pelletizer, or the melt-kneaded product or the sheet-like form is put into the hopper port of the extruder, and the sheet is also formed by the extruder. It is possible to make it into a layer, and in this case, it can be laminated on the surface of the laminate by the same method as described above.

"Examples" Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. The physical properties described in the following examples were measured as follows.

Gel content: The surface layer sheet was placed in a 350 mesh wire net and immersed in tetrahydrofuran boiled in a constant temperature water bath at 80 ° C. for 4 hours to obtain the content.

Heat resistance: It was determined from the time during which a lit cigarette was left horizontal on the surface of the obtained laminate and the time when the surface irregularities were deformed or the surface was melted and deformed.

Abrasion resistance: The sheet obtained by calender molding was determined by a Taber abrasion tester using an abrasion wheel H-18, and the loss of abrasion after 1,000 rotations under a load of 500 g.

Calender processability: A cross-linkable soft vinyl chloride composition blended with a ribbon blender was kneaded with a Banbury mixer at 150 ° C for 5 minutes, and then with an inverted L-type calender, the fourth roll was set to 160 ° C and the thickness was about 0.5 mm. The transparent sheet was prepared and the workability was evaluated from the surface condition of the sheet.

Examples 1 to 3 As shown in Table 1, in a ribbon blender, vinyl chloride resin (“Kanevinyl S1003” manufactured by Kanebuchi Chemical Co., Ltd.) 100 parts (parts by weight, the same applies hereinafter), DOP, epoxidized soybean oil, Ba- Zn
A system stabilizer, dibutyltin dilaurate, and stearic acid were added, and finally, a silyl group-containing vinyl polymer (γ-methacryloxypropyltritrimethoxysilane 10 parts, methyl methacrylate 55 parts, allylic acid n-butyl 35 parts was added to xylene.
Obtained by polymerizing at 120 ° C. using azobisisobutyronitrile as an initiator in 100 parts. ) Is blended, immediately put into a Banbury mixer, and kneaded at 150 ° C for 5 minutes, and then the fourth roll is set to 160 ° C with an inverted L-type calender to have a thickness of about 0.5.
I made a mm transparent sheet.

The transparent sheet obtained by the above method is laminated on the foamed plastisol layer which is semi-gelled on non-combustible asbestos paper, 20
It was heated in an oven at 0 ° C. for about 3 minutes to form a foamed laminate having good cushioning properties.

Using the obtained laminate, the tobacco resistance test, the gel content of the surface layer, the abrasion resistance and the calendering workability were evaluated, and the results are shown in Table 1.

From Table 1 it can be seen that the laminate according to the invention is
It has a heat resistance of 180 seconds or more, and it can be seen that the heat resistance is extremely good.

Comparative Example 1 The silyl group-containing vinyl polymer was not added, the other compounding ingredients were the same as in Example 1, the compounding agents were blended and processed under the same conditions to prepare a sheet, and a laminate was prepared by the same method to obtain physical properties. Was measured.

The surface layer of this laminate melted the surface when a lit cigarette was left for 30 seconds to cause unevenness.

Comparative Example 2 Using a 20 polymerization machine, 150 parts of deionized water, 0.1 part of polyvinyl alcohol, 0.05 part of isobutyl peroxydicarbonate and 0.2 part of diallyl phthalate were charged, and after degassing, 100 parts of vinyl chloride monomer was charged and stirring was started. Then, the temperature was raised to 40 ° C. and polymerization was carried out for 17 hours. After the completion of the polymerization, the contents were taken out and dehydrated and dried. To 100 parts of the obtained vinyl chloride polymer (tetrahydrofuran-insoluble gel content 30%), the compounding agent as shown in Table 1 was added and blended with a ribbon blender. After that, knead in a Banbury mixer at 165 ° C for 5 minutes and set the fourth roll at 185 ° C by an inverted L-type calender to about
A 0.5 mm thick transparent sheet was created. Hereinafter, a laminate was prepared and physical properties were measured by the same method as in the examples.

The surface layer of this laminate melted and became uneven when a lit cigarette was left for 70 seconds.

"Effect of the invention" The present invention makes it possible to simultaneously carry out the crosslinking reaction by the silyl group and the melting of the vinyl chloride resin by using the vinyl oligomer in the main chain portion of the silyl group-containing compound, and to carry out the crosslinking. The transparent soft vinyl chloride resin sheet can be easily manufactured by calendar molding or extrusion molding. By heat-treating the sheet to form a surface layer, heat resistance is significantly improved and abrasion resistance is also good. Therefore, the performance of the laminate can be significantly improved.

Claims (2)

[Claims] 1. A laminate having excellent heat resistance, comprising a resin composition sheet comprising the following components (a), (b) and (c) as a surface layer; Resin 100 parts by weight, (b) Obtained by hydrosilylation reaction of vinyl resin having carbon-carbon double bond and hydrosilane, or radical copolymerization of vinyl compound and radically polymerizable silane compound having double bond The following general formula (In the formula, R is hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms selected from alkyl, aryl and aralkyl groups, X
Is a hydrolyzable group, and n is an integer of 1 to 3) and is a vinyl polymer having at least one silyl group in the molecule.
3 to 150 parts by weight, (c) plasticizer 30 to 200 parts by weight 2. The resin composition sheet comprises, as a silanol catalyst, 0.01 or more dibutyltin compounds selected from the group consisting of dibutyltin laurate, dibutyltin diacetate, dibutyltin dioctanoate and dibutyltin phthalate.
The laminated body according to claim 1, containing 5 to 5 parts by weight.