JPH01163040A - Production of polyvinyl chloride laminated product - Google Patents

Abstract

PURPOSE:To reduce the number of manufacturing processes to a large extent and to enhance the bonding reliability between a main body layer and a cushion layer to a large extent, by simultaneously performing the integral molding of the main body layer and the cushion layer formed to the back surface of the main body layer. CONSTITUTION:The material of a cushion layer mainly consists of 100 pts.wt. of polyvinyl chloride, crosslinked PVC being a copolymer with 0.01-20 pts.wt. of a vinyl monomer containing active hydrogen or an epoxy group, polyisocyanate or a mixture or reaction product of polyisocyanate and polyol, a plasticizer and a foaming agent and the compounding amount of polyisocyanate to 100 pts.wt. of crosslinked polyvinyl chloride is 0.007-100 pts.wt. Further, polyisocyanate is selected from one or more kind of monomeric polyisocyanate, adduct polyisocyanate, polymerized polyisocyanate and masked polyisocyanate and polyol is selected from one or more kind of short chain polyol and long chain polyol.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is characterized in that a main body layer and a cushion layer formed on the back surface of the main body layer are simultaneously integrally molded to form polyvinyl chloride (PVC).
Regarding the method of manufacturing laminate products, it is a suitable method for manufacturing, for example, side moldings for automobiles, wall sheets for interior rooms, and the like.

In this specification, explanation will be given using a side molding as an example, but the invention is not limited to this.

<Prior Art> The general structure of a side molding having a cushion layer on the back side is as shown in FIG. Using a double-sided adhesive tape (hereinafter referred to as "double-sided tape") 3 formed with
4 (Utility Model No. 60-140740)
(Refer to Utility Model Application No. 59-29830). In the illustration,
5 is an insert, and 6 is a protective paper. The material of the molding body 4 is usually PvC, but the material of the base film 1 of the double-sided tape is highly foamed (foaming ratio 10
2 times or more: the same applies hereinafter) are possible soft polymer materials such as polyethylene, chloroprene rubber, acrylic rubber, etc. Also,
The adhesive has viscoelastic properties at room temperature and exhibits strong adhesion to both the adherend (vehicle body and molding body) and the base film, and is usually acrylic or rubber-based.

<Problems to be Solved by the Invention> As mentioned above, in manufacturing the molding, the molding body (main body layer) and the double-sided tape (cushion layer) are molded separately and then bonded and integrated, which requires a large number of manufacturing steps. Furthermore, since the molding body and the cushion layer are made of different materials, the reliability of the adhesion is insufficient, and peeling occurs between the back of the molding body and the double-sided tape, especially after long periods of use on an actual vehicle. The problem was that it was easy to do.

Means for Solving the Problems In order to solve the above problems, the inventors of the present invention made extensive efforts in development, and as a result, they came up with a method for manufacturing polyvinyl chloride laminates having the following configurations.

The method for producing a polyvinyl chloride laminate according to claim 1,
When simultaneously integrally molding the main body layer and the cushion layer formed on the back surface of the main body layer, as materials for the cushion layer: (1) 100 parts by weight of vinyl chloride and 0.01 to 20 parts by weight of a vinyl monomer containing active hydrogen or an epoxy group. Mainly consisting of crosslinkable PvC1, which is a copolymer with parts by weight, and (1) polyisocyanate or a mixture or reaction product of polyisocyanate and polyol, and (2) a plasticizer and a blowing agent, based on 100 parts by weight of crosslinkable polyvinyl chloride. A polyisocyanate containing 0.007 to 100 parts by weight is used, and the polyisocyanate is monomeric polyisocyanate (excluding when used alone), adduct polyisocyanate, polymerized polyisocyanate, and masked polyisocyanate. , and the polyol compound is a short chain polyol (
However, alone! #Excluding combinations with polymeric polyisocyanates. ) or long-chain polyols.

Furthermore, the method for manufacturing a polyvinyl chloride laminate according to claim 2 is characterized in that the reaction product of the polyisocyanate and polyol is further acrylic-modified in the manufacturing method according to claim 1. .

Detailed explanation of the configuration The above configuration will be explained in more detail.

Note that "parts" indicating the number of parts to be blended means "parts by weight" unless otherwise specified.

(1) The crosslinkable PVC used in the present invention is vinyl chloride 1
00 parts by weight, a vinyl monomer containing active hydrogen or an epoxy group (hereinafter referred to as "functional vinyl monomer")
It is obtained by copolymerizing 0.01 to 20 parts (preferably 0.5 to 4 parts). Functional vinyl monomer is 0.01
If the amount is less than 20 parts, there will be too few crosslinking points and it will be difficult to obtain a highly foamed cushion layer, and if it exceeds 20 parts, the number of crosslinking points will be too large, resulting in a hard foam that will no longer function as a cushion layer.

The above-mentioned functional vinyl monomers include: (1) dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, nadic acid, succinic acid, and cis-Δ4-tetrahydrophthalic acid, and their anhydrides, (2) acrylic acid, crotonic acid, methacrylic acid, and maleic acid. Acid monoesters, nadic acid monoesters Monocarboxylic acids such as cinnamic acid and vinyl formate, ■Hydroxycarboxylic acids such as hydroxyethyl acrylate and hydroxypropyl acrylate, ■Acid amides such as N-methylol acrylamide, ■Vinyl cyclohexene monoxide Examples of epoxy compounds such as
Of course, vC may be copolymerized with other vinyl monomers such as vinyl acetate. In addition, when vinyl acetate is copolymerized,
It has the effect of inhibiting thermal decomposition of PVC.

(2) The polyisocyanate used in the present invention is as follows:
It is selected from one or more of monomeric polyisocyanates, adduct polyisocyanates, polymerized polyisocyanates, and masked polyisocyanates. However, except for (1), these polyisocyanates are used alone or as a reaction product mixed or reacted with a polyol described below at a predetermined ratio.

■ Monomeric polyisocyanate: 4.4'-diphenylmethane diisocyanate (abbreviation r
MDIJ), hydrogenated 4,4'-diphenylmethane diisocyanate (abbreviation "Water IMDIJ"), tolylene diisocyanate (abbreviation rTDIJ), isophorone diisocyanate (abbreviation rIPDIJ), 1,5-naphthalene diisocyanate (abbreviation "NDIJ"), xylene diisocyanate (abbreviation " XDIJ), hydrogenated xylene diisocyanate (abbreviated as "water tliXDIJ"), 1,6-hexamethylene diisocyanate, 4.4',4'-triphenylmethane triisocyanate, tris(P-isocyanate phenyl) thiophosphate, etc. .

■Adduct polyisocyanate: The calculated amount of monomeric polyisocyanate listed in ■ above,
It is obtained through an addition reaction with triols such as trimethylolpropane and glycerin, and has a lower vapor pressure than monomeric polyols, making it easier to handle from a safety standpoint.

■Polymerized polyisocyanate: It is obtained by trimerizing and terminating the monomeric polyisocyanates mentioned above, and as mentioned above, it has a lower vapor pressure and is easier to handle than the monomeric polyisocyanates. It also has good heat resistance and high reactivity.

(2) Masked polyisocyanate: These are monomeric polyisocyanates, adduct polyisocyanates listed in (1) above, and polymerized polyisocyanates listed in (2) whose NGO groups are temporarily protected with a masking agent. Here, examples of the masking agent include phenol, diethyl malonate, acetoacetate, acetylacetone, cyclohexanone oxime, thiophenol, aliphatic alcohol, cyanogenic sodium sulfite, and the like. Masked polyisocyanate is used by raising the temperature to a predetermined temperature as necessary to regenerate the NCO groups, and has good storage stability and excellent handling from the viewpoint of reaction control.

(3) The polyol used in the present invention is selected from one or more of the following: (1) short chain polyols or (2) long chain polyols.

These polyols are mixed or reacted with the above-mentioned polyisocyanate at a -NCOloH ratio and used as a reaction product.

■Short chain polyol: ethylene glycol (abbreviation rEGJ), glycerin, 1
．． 4-butanediol (abbreviation r1.4BDJ), 1.6
-Hexanediol (abbreviation "1゜6HDJ), 1.s-
Bentanediol (abbreviation "1.5PDJ") and the like can be mentioned.

However, it should not be used alone in combination with monomeric polyisocyanate (it may be used in combination with other long-chain polyols).

■Long chain polyol: (i) Polypropylene glycol (abbreviation rPPG),
Polytetrabutylene glycol (PTG), polyethylene glycol, polypropylene ethylene glycol,
Polyether polyols such as propylene oxide/glycerin reactants and propylene oxide/trimethylolpropane reactants.

(i I) Polyethylene adipate (abbreviation rPEAJ)
, polypropylene adipate, polybutylene adipate (abbreviation "PBA"), polyethylene bu.

Polyester polyols such as tyrene adipate (abbreviated as rPEBA).

(lli) Acrylic polyol obtained by reacting a polymer of acrylic acid ester with a short chain polyol, and (lv) Liquid epoxy resin (molecular weight 500-2000)
Examples include epoxy polyols in which amino diols are added to epoxy groups at both ends.

(4) Each of the polyisocyanates in component (2) above can be used alone, except for the monomeric polyisocyanate.

Furthermore, one or more of component (2) can be mixed with one or more of each polyol of component (3) as appropriate, or used as a reaction product. At this time, the NGO
The 10H ratio is 1.1 when final NGO is used.
~F, when final OH is used, 0.7 to 0.9
8.

Furthermore, it is also possible to polyadd an acrylic monomer such as methyl methacrylate (MMA) or ethyl methacrylate (EMA) to these reaction products (polyurethane) for acrylic modification.

(5) The blending amount of the component (3) above with respect to the crosslinkable pvctoo part is 0.007 to 100 (preferably 0°00
If the amount is less than 0.007 parts, there will be almost no crosslinking and it will be difficult to obtain a highly foamed cushion layer;
If it exceeds 0 parts, it will become a hard foam and will no longer function as a cushion layer.

(6) As the above-mentioned plasticizer, ■phthalate esters such as di-2-ethylhexyl phthalate (abbreviation rDOPJ), di-n octyl phthalate (abbreviation rn-DOPJ), dinonyl phthalate, diisodecyl phthalate, and diisodecyl phthalate; ■ Di-2-ethylhexyl adipate (abbreviation "DOA"), di-n-octyl adipate,
Aliphatic dibasic acid esters such as di-2-ethylhexyl sebacate, ■phosphate esters such as trioctyl phosphate and triphenyl phosphate, ■epoxys such as epoxidized soybean oil, ■trioctyl trimellitate, etc. Examples include aromatic carboxylic acids, which can be used alone or in combination of two or more.

The amount of this plasticizer added to the crosslinkable pvctoo portion is 40 to 100 parts.

(7) As blowing agents, ■ azobisisobutyronide nitrile (abbreviation: rAZIBJ), azodicarbonamide (abbreviation: rADcAJ), benzenesulfonyl hydrazide (abbreviation: rADcAJ),
abbreviation “BSH”), trihydrazinotriazine (abbreviation r
Examples include organic types such as T) (TJ), N,N'-dinitrosopentamethylenetetramine (abbreviation [DPTJ), and inorganic types such as sodium bicarbonate, sodium borohydroxide, and ammonium carbonate. Note that for DPT, a foaming aid (organic acid or urea) is used in combination to promote decomposition and lower the decomposition temperature.

The amount of this blowing agent relative to the crosslinkable pvctoo part is:
In order to obtain a highly foamed product, the amount is usually 0.5 to 5 parts.

(8) For the above-mentioned crosslinkable PVC, a stabilizer is usually added for the purpose of improving heat resistance and light resistance, and further,
Add auxiliary materials such as lubricants, ultraviolet absorbers, and antioxidants as appropriate.

The above-mentioned stabilizers include (1) metal soaps such as metal salts (Ca, Ba, Pb, Zn, etc.) such as steric acid and lauric acid; (2) dioctyltin dilaurate, dioctyltin maleate, dibutyltin dilaurate, dibutyltin maleate, and dibutyl; Examples include tin-based stabilizers such as tin mercapto, and lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, tribasic lead maleate, and dibasic lead sulfate. Use a mixture of two or more types.

(9) In addition, the main body layer is made of ordinary PVC, the above plasticizer,
A PVC compound containing a stabilizer, a lubricant, a filler, a pigment, an ultraviolet absorber, an antioxidant, and a blowing agent as appropriate is used.

(lO) The PVC laminate of the present invention is produced by simultaneously molding the main body layer (molding main body) 4 and the cushion layer IA by extrusion or injection using the above-mentioned materials (see FIG. 1). At this time, the main body IW4 and the cushion [IA] are made of the same PVC material, so there is no need to use an adhesive layer (adhesive layer) as in the past.
Fused and completely integrated.

In the case of the side molding shown in FIG. 1, an adhesive layer 2 is formed on the front side of the cushion layer IA, and the cushion layer IA is further covered with a protective paper 6 in order to be attached to the vehicle body.

<Effects of the Invention> The method for manufacturing a PVC laminate product of the present invention has the following effects due to the above configuration.

(a) Because the main body layer and cushion layer are simultaneously integrally molded,
Compared to the conventional manufacturing method in which the main body layer and the cushion layer are molded separately and then bonded together, it is possible to significantly reduce the number of man-hours required to manufacture PVC laminates. (b) The main body layer and the cushion layer are made of the same material. Since the main body layer and the cushion layer are fused together, the reliability of the adhesion between the main body layer and the cushion layer is higher than in the conventional case where the main body layer and the cushion layer made of different materials are integrated via an adhesive layer. is significantly improved.

<Examples> Hereinafter, the present invention will be described in further detail based on Examples.

Main body layer materials with the following compositions and Table 1 - (1), (2)
, (3).

(4) The cushion layer material having the composition shown in FIG.
, wlmm) to obtain laminates of each example and comparative example.

In addition, each crosslinkable PvC in Table 1 was obtained by copolymerizing a monomer mixture having the composition shown in Table 2 by a conventional method. In addition, each masked polyisocyanate compound in Table 1-(2) is obtained by masking the monomeric polyisocyanate shown in Table 113 with each masking agent, and the urethane polymer in Table 1-(3) is It was obtained by mixing the long-chain polyol shown in Table 4 and polyisocyanate, reacting in N2 gas at 180°C for 3 hours, and then adding the short-chain polyol shown to cause a chain extension reaction. .

Furthermore, the acrylic modified polyurethane in Table 1-(4) was obtained by reacting the polyurethane obtained by the above method with the formulation shown in Table 4 at 80°C for 8 hours with the formulation shown in Table 5. This is what I got.

(11 Main body layer material PVC (p=1450) 100 parts DOP
80 parts epoxidized soybean oil 3 parts tree n-
Octyl tin acetate 4.5 parts The following tests were conducted on the laminates of each of the Examples and Comparative Examples obtained above. Regarding the test results, Table 1 - (1), (2)
, (3) and (4).

In all of the examples, the cushion layer exhibited a good appearance with little waviness and exhibited high peel strength, but in all of the comparative examples, large waviness occurred in the cushion layer.
Moreover, the peel strength was also low.

In addition, Comparative Examples 1, 6, 10, 14 and 2, 7, 11, 1
5 is an example in which the amount of polyisocyanate compound blended is too little or too much, Comparative Examples 3, 8, 12, 16 and 4, 9,
Samples No. 13 and 1 are examples in which the content of activated vinyl chloride in crosslinkable PvC is too little or too much, respectively, and Comparative Example 5 is an example in which general-purpose PvC without crosslinkability was used as PVC.

(1) Cushion layer foaming ratio: 30 CmX 30 CmX Thickness (C-) Weight (g)
was measured and calculated using the following formula. The PvC specific gravity is 1.2
And so.

(2) Cushion layer appearance: Visually determined.

Items with large undulations...× Items with small undulations...○ (3) Peel strength: Tensilon tensile speed 30II
A T-peel test was performed at 1/min.

Table 2 Table 3 Table 4 Table 5

[Brief explanation of the drawing]

Figure 1 shows a side view of an example of the PVC laminate product of the present invention.
FIG. 2 is a partially cutaway perspective view of a conventional side molding, and FIG. 3 is a cross-sectional view of the extruded test piece. 1...Cushion layer. 2...Adhesive layer (adhesive layer), 4...Mall body (main body layer). Patent application Voluntary amendment procedure supplementary device 63.6.01 Showa year, month, day 1, case description 1988 Patent application No. 095327 2, name of invention Method for manufacturing polyvinyl chloride laminate products 3, Relationship to the case of the person making the amendment Patent application Person's address name Toyoda Gosei Co., Ltd. 4, agent 6 Contents of amendment (1) Table 1 on page 22 of the specification - (0 will be amended as shown in the attached sheet) (2) Table 4 on page 25 of the same document shall be amended as shown in the attached sheet.

Claims (1)

[Claims] 1. A method for manufacturing a polyvinyl chloride laminate product by simultaneously integrally molding a main body layer and a cushion layer formed on the back surface of the main body layer, comprising: (1) as a material for the cushion; ) A crosslinkable polyvinyl chloride which is a copolymer of 100 parts by weight of vinyl chloride and 0.01 to 20 parts by weight of a vinyl monomer containing active hydrogen or an epoxy group, and (2) a copolymer of polyisocyanate or a polyisocyanate and a polyol. A mixture or a reaction product, and (3) a plasticizer and a blowing agent are used, and the amount of the component (2) is 0.007 to 100 parts by weight based on 100 parts by weight of the component (1). Furthermore, the polyisocyanate is selected from one or more of monomeric polyisocyanates (excluding those used alone), adduct polyisocyanates, polymerized polyisocyanates, and masked polyisocyanates, and the polyol is a short-chain polyisocyanate. It is selected from one or more types of polyols (excluding combinations alone with monomeric polyisocyanates) and long-chain polyols. A method for producing a polyvinyl chloride laminate product, characterized by: 2. The method for producing a polyvinyl chloride laminate according to claim 1, wherein the reaction product of the polyisocyanate and the polyol is further modified with an acrylic monomer.