JPH04279676A - Protecting material of vinyl chloride base - Google Patents

Abstract

PURPOSE:To obtain a protecting material of PVC base improving bond strength in an ordinary state and water-resistant bond strength while suppressing the addition amount of bond strength imparter to a very small amount, while yet developing sufficient peel strength even by baking at low temperature without causing change of color. CONSTITUTION:A polyvinyl choloride is blended with at least a plasticizer among the plasticizer, a filler and other ordinary additives to give a polyvinyl chloride plastisol as a base material and the polyvinyl chloride plastisol is mixed with a bond strength imparter obtained by mixing an aminosilane compound with an epoxy compound.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention is directed to applying an epoxy resin to the surface of various parts, such as the underbody of an automobile, which is made by electrodepositing an epoxy resin onto a metal plate such as a steel plate. or metal plate or PE
Apply directly to the surface of plastic such as T-film,
The present invention relates to a vinyl chloride-based protective material that has a function of protecting these adherends, especially a rust-preventing function. [0002] Generally, this type of protective material uses polyvinyl chloride plastisol (hereinafter referred to as PVC sol) as a basic material, which is a mixture of polyvinyl chloride (PVC), a plasticizer, and a filler. To this, appropriate amounts of other general additives such as a PVC stabilizer, an adhesive force imparting agent, a coloring agent, a thixotropic agent, etc. are added. PVC like this
In recent years, sol-based protective materials have come to be widely used as paints for underbody protective coatings of automobiles, but in order to proceed with the development of a wider range of application fields, there is a demand for quality improvements using trace amounts of additives. is increasing. [0003] Particularly, as with the above-mentioned automobile underbody protective coating paint, it is used under conditions where the usage environment such as weather and temperature fluctuates drastically and where large mechanical external forces such as peeling force are applied to the paint film. In this case, it is strongly desired to provide strong adhesive force to the underlying surface coated with electrodeposition coating. By the way, among the above-mentioned general additives,
Conventionally, as an adhesive force imparting agent for imparting adhesive force to PVC sol, one type of organic silicon/titanium compound type, including epoxy resin type, polyurethane resin type, polyamide type, aminosilane type, and organic sulfur compound type is used. Adhesive agents were selected and used. Among these, epoxy and polyurethane resins were most commonly used. [Problems to be Solved by the Invention] However, as mentioned above, in the conventional PVC-based protective material made by adding only one type of adhesive force-imparting agent to the PVC sol, during storage after manufacture, The viscosity changes and the decrease in adhesive strength over time are large, and the decrease in water-resistant adhesive strength is particularly remarkable. Therefore,
It is difficult to provide the adhesive strength, that is, the peel strength, required for the above-mentioned automotive underbody protective coating paint. [0006] In addition, in order to develop sufficient adhesive strength,
It is possible to increase the amount of adhesion imparting agent, but
By increasing the amount added in this way, the normal adhesive strength and water resistant adhesive strength can be improved to some extent, but compared to the number of parts added,
The improvement effect is small, and the improvement in adhesive strength is small in comparison to the increase in cost, and the change in viscosity over time becomes even greater. In addition, ordinary amine-based adhesives are subject to severe discoloration over time, not only during baking but also after application, making them unsuitable for use in parts such as automobiles that require a good finished appearance. It was something that didn't exist. The present invention was developed through intensive research in view of the above-mentioned circumstances, and has been developed to achieve excellent normal adhesive strength and water-resistant adhesive strength while minimizing the amount of adhesion imparting agent added. The object of the present invention is to provide a PVC-based protective material that can exhibit sufficient peel strength even when baked. [Means for Solving the Problems] In order to achieve the above object, the PVC-based protective material according to the present invention contains at least a plasticizer among plasticizers, fillers, and other general additives in PVC. The PVC sol is a basic material, and an adhesive force imparting agent made of an aminosilane compound and an epoxy compound is added to the PVC sol. In particular, when PVC is 100 parts by weight,
40-400 parts by weight of plasticizer, 0-1000 parts of filler
It is desirable to mix the other additives in a proportion of 0 to 200 parts by weight, and the adhesive force imparting agent in a proportion of 0.05 to 10 parts by weight. [0010] Each material used in the present invention will be explained in detail below. The paste resin that is a component of PVC sol is P with a degree of polymerization of 700 to 3500.
In the case of a homopolymer using straight VC, and in the case of a copolymer, that is, an ethylene-vinyl acetate-vinyl chloride terpolymer (PVC-
EVA) may be used. Examples of plasticizers include organic acid (including fatty acids)-alcohol esters, phosphoric acid esters, silicate esters, epoxidized fatty acids, and other known plasticizers such as chlorinated paraffins and alkyldiphenyl. One type or a mixture of two or more types can be used. Specific examples of the organic acid (including fatty acids)-alcohol esters include monovalent organic acids and monovalent alcohols, monovalent organic acids and polyvalent alcohols, polyvalent organic acids and monovalent alcohols, There are polyhydric organic acids and polyhydric alcohols, etc.
Specific examples of phosphoric acid esters include phosphoric acid and monohydric alcohols, phosphoric acid and monohydric phenols, phosphoric acid and monohydric phenols/monohydric alcohols, etc. Specific examples of silicic esters include , silicic acid and monohydric alcohols, silicic acid and monohydric phenols, etc. Paste resin 10
0 parts by weight, 40 to 400 parts by weight are blended. Fillers include heavy/light calcium carbonate, silica, talc, clay, alumina, and mica, and have a powder size of 200 mesh (particle size 5
0 to 100 μm), and 0 to 1000 parts by weight are blended per 100 parts by weight of paste resin. Other general additives include PVC stabilizers such as primary stabilizers, secondary stabilizers, and other polymeric stabilizers; deterioration inhibitors such as ultraviolet absorbers and antioxidants; and inorganic Examples include coloring agents such as pigments, organic pigments, and dyes, and thixotropic agents such as asbestos, colloidal silica, cellulose, sepiolite, and magnesium compounds.
Specific examples of secondary stabilizers include organic acid metal salts, inorganic acid metal salts, mercaptan thioethers, and compounds of their derivatives and metals. Specific examples of secondary stabilizers include epoxy compounds, phosphorous acid, etc. There are esters, etc.
Specific examples of other polymeric stabilizers include organic nitrogen compounds. Specific examples of ultraviolet absorbers include alkylphenols, alkylphenol-benzotriazoles, etc. Specific examples of antioxidants include alkylphenols, organic nitrogen compounds, peroxide decomposers (sulfur, phosphorus, selenium, etc.). These general additives are blended in an amount of 0 to 200 parts by weight per 100 parts by weight of paste resin. [0014] In addition, among the quality improvements of this type of protective materials, adhesive strength imparting agents that contribute to the most highly demanded improvement in adhesive strength include epoxy resins, polyurethane resins, organic sulfur compound systems, and polyamides. Conventionally, one type of them has been selected and used, but in the present invention, an adhesive force-imparting agent made by preparing and blending an aminosilane-based compound and an epoxy compound is used. It is used in an amount of 0.05 to 10 parts by weight per 100 parts by weight of paste resin. Specific examples of the aminosilane compounds used in the present invention include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethyldimethoxysilane, and γ-aminopropylmethyldimethoxysilane. Ethoxysilane, N-(
β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ
-aminopropylmethyldimethoxysilane, N-(β-
There are other aminosilane compounds such as aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-(diaminodiethyl)-γ-aminopropyltrimethoxysilane, and specific examples of epoxy resin compounds include:
Bisphenol A diglycidyl ether (epoxy equivalent EEW = 170-2200), bisphenol F diglycidyl ether (EEW = 156-190), phenol novolak type polyglycidyl ether (EEW = 1)
70-200), alkylphenol novolac type polyglycidyl ether (EEW=170-250), N
, N,N'N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyldiaminodiphenylmethane, phthal There are acid diglycidyl ester, phenyl glycidyl ether, cresyl glycidyl ether, and other aromatic and epoxy compounds having a cyclohexyl group. Further, the amount and method for preparing the adhesive force imparting agent used in the present invention are as follows. Blend amount: 0.01 to 1.0% of epoxy resin monomer alone or in combination of several types per 1 mole of aminosilane.
0 equivalents are reacted. Reaction method: A 500 ml four-necked flask is equipped with a stirrer, a thermometer, a nitrogen sealing port, and a sample inlet, the flask is sealed with nitrogen, and 1 mol of aminosilane is charged. Next, heat the flask until the internal sample temperature reaches 30~
Adjust the temperature to 80°C. Then, an epoxy resin monomer that has been heated or mixed in advance to have a viscosity of 1000 cps or less is gradually added dropwise to cause a reaction. After the heat generated by the reaction subsides, the mixture is heated and maintained at 80° C. for 1 hour or more to complete the reaction. Note that this adhesive force imparting agent may be added to and mixed with the PVC sol immediately after blending the adhesive force imparting agent without pre-reacting in advance. [0017] The PVC-based protective material having the above-mentioned structure is used, for example, as a paint for protecting various parts of an automobile as shown in FIG. In Figure 1, 1 is the entire lower body part and the underbody part such as the wheel house, 2 is the intermediate part such as the rocker panel and front apron, and 3 is the outer surface part of the vehicle body. Rust prevention is applied by baking onto the electrodeposited coating film 5 of resin such as vinyl chloride, urethane, or polyester, which has been formed in advance on the surface of the metal plate 4 such as a steel plate constituting the painted area. A coating film 6 is formed, thereby achieving a rust prevention function for each of the above-mentioned parts. Here, in the present invention, as the adhesive force imparting agent added to the above-mentioned protective material, by using an adhesive force imparting agent made by blending an aminosilane type compound and an epoxy compound, conventional epoxy resin type, polyurethane type Compared to using a single adhesion agent such as a resin-based adhesive, it has excellent not only normal adhesive strength but also water-resistant adhesive strength, and because the required amount is reduced, it reduces costs and provides sufficient peeling even when baked at low temperatures. It is possible to form a coating film that exhibits strength and has excellent discoloration properties. [Example] Examples No. 1 to No. 32 of the present invention and Comparative Examples No. 1 to No. 6 will be explained below. (1) Basic composition of materials used: Paste resin (Zeon 38J)
100 parts by weight
Plasticizer (dioctyl phthalate; D
OP) 150 parts by weight
Filler (manufactured by Nitto Funka; NS-100)
100 parts by weight
Adhesion agent
variable
(2) Baking conditions: 120℃ x 2
0 minutes (3) Preparation of adhesive force imparting agent: Using aminosilane and epoxy resin monomer, according to the blending amount and reaction method as described above. (4) Adhesive force imparting agent for comparative example: 1) γ-aminopropyltrimethoxysilane 2) N-(
β-aminoethyl)-γ-aminopropyltrimethoxysilane (5) Adhesive agent for examples: 1) γ-aminopropyltrimethoxysilane
179.4 g (1 mol) Bisphenol A diglycidyl ether 36.0 g (
0.19 equivalents) 2) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane
22
2.4 g (1 mole)
Bisphenol A diglycidyl ether 22
．． 3 g (0.1174 equivalent) 3) N
-(β-aminoethyl)-γ-aminopropyltrimethoxysilane

222.4 g (1 mole)
Bisphenol A diglycidyl ether 44.5 g (0.234 equivalent)
4) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane

222.4 g (1 mole)
Bisphenol A diglycidyl ether 66.7 g (0.35 equivalent)
5) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane

222.4 g (1 mol) Bisphenol A
Diglycidyl ether 89.0 g (0.468
4 equivalents) 6) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane

222.4 g
(1 mol) Bisphenol F diglycidyl ether 39.0 g (
0.232 equivalents) 7) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane
22
2.4 g (1 mole)
Phthalate diglycidyl ester
37.4 g (0.234 equivalent)
8) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane

222.4 g (1 mole)
m,p-cresyl glycidyl ether 40.5 g (0.245 equivalent)
9) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane

222.4 g (1 mol) Phenyl glycidyl ether 71.4 g (
0.476 equivalents) 10) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane

222
．． 4 g (1 mole)
1,3-bis(N,N-diglycidylaminomethyl)
cyclohexane

22.5 g (0.245 equivalent)
11) N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane

222.4 g (1 mole)
Bisphenol A diglycidyl ether 22.3 g (0.0113 equivalent) 12) N-(β-aminoethyl)-γ-
Aminopropyltrimethoxysilane

264.4 g (1 mol) Bisphenol A diglycidyl ether 44.5 g (0.23
4 equivalents) 13) N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane

206.4
g (1 mol) Bisphenol A diglycidyl ether 44.5 g (0.
234 equivalents) In each of the comparative examples and examples manufactured using the above-mentioned materials, changes in relative viscosity and 90° peel strength ( JIS C
6481) and water resistance 90° peel strength were measured. Comparative examples and examples, including the measurement results, are shown in Tables 1 to 1 below.
5. The amount added is 350g of PVC sol (PV
The relative viscosity change is the viscosity change when the viscosity immediately after manufacture is set to 1. Value measured after leaving it in the sun (unit: g/cm
), and the water resistance 90° peel strength is a value measured in the same manner as above, after baking and cooling, immediately after being immersed in water for 7 days. [Table 1] [Table 2] [Table 2] [Table 3] [Table 3] [Table 4] [Table 5] [Table 5] The adhesive force imparting agent is added to and mixed with the PVC sol immediately after the adhesion imparting agent is blended without pre-reacting in advance.
Even in this case, during storage and baking, Example No.
Almost the same reaction product as in the cases up to No. 24 is produced, and exhibits particularly excellent adhesive strength with excellent water resistance. As is clear from the above-mentioned Examples and Comparative Examples and their measurement results, the storage stability of the PVC sol after the addition of the adhesive force-imparting agent was determined in the accelerated test at 45°C. In the case of each example, an increase in viscosity and a decrease in adhesive strength were observed, but there was almost no change in storage stability at room temperature, so although it is very sensitive to temperature changes, overall Storage stability was good. In addition, compared to the comparative example, it can be seen that not only the normal adhesive strength but also the water-resistant adhesive strength is excellent, and sufficient adhesive strength can be obtained even when baking at a low temperature. [0028] Furthermore, as the amount of adhesion imparting agent, PV
If the amount is less than 0.5 parts by weight based on 100 parts by weight of C,
It is insufficient in terms of 90° peel strength, and if the amount is 10 parts by weight or more, the degree of increase in peel strength with respect to the increase in the amount added is very low, and the effect is small considering the increase in cost. Therefore, it can be seen that the most preferable addition range is 0.5 to 10 parts by weight per 100 parts by weight of PVC. As described above, according to the present invention, by using a mixture of an aminosilane compound and an epoxy compound as an adhesive force imparting agent, conventional epoxy resins and polyurethane Compared to the case of using a single adhesion agent such as a resin-based adhesive, during storage after manufacturing, changes in viscosity and decrease in adhesive strength over time are minimized, and not only normal adhesive strength but also water-resistant adhesive strength is improved. It is possible to improve the Moreover, even if the amount of adhesion imparting agent is reduced, it is possible to develop sufficient peel strength, which not only reduces costs due to the reduction in the amount of adhesion imparting agent added, but also enables low-temperature baking and prevents discoloration. It is also possible to form an excellent coating film. Therefore, like a car,
It is also suitable for use in areas that are used under harsh environmental conditions and where good appearance is required, and has the effect of expanding the scope of application.

[Brief explanation of the drawing]

1 is a diagram illustrating various parts of an automobile that utilize the PVC-based protective material according to the present invention; FIG.

FIG. 2 is an enlarged sectional view of each part in FIG. 1.

[Explanation of symbols]

1 Underbody part 2 Middle part 3. External part of the vehicle body 4 Metal plate 5 Electrodeposition coating film 6 Anti-rust coating

Claims (2)

[Claims] [Claim 1] While the basic material is polyvinyl chloride plastisol, which is made by blending polyvinyl chloride with at least a plasticizer, fillers, and other general additives, it also contains an aminosilane compound and an epoxy compound. A vinyl chloride-based protective material, characterized in that an adhesive force imparting agent comprising the following is added to the above-mentioned polyvinyl chloride plastisol. 2. When polyvinyl chloride is 100 parts by weight, the plasticizer is 40 to 400 parts by weight, and the filler is 0 to 1 part by weight.
2. The vinyl chloride-based protective material according to claim 1, wherein the vinyl chloride-based protective material contains 0.000 parts by weight, 0 to 200 parts by weight of other additives, and 0.05 to 10 parts by weight of an adhesive force imparting agent.