JP2811346B2 - Manufacturing method of polyacetal resin laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyacetal resin laminate in which a synthetic resin coating layer is strongly adhered to a polyacetal resin surface.

(Prior art) Polyacetal resin has mechanical strength, creep properties,
It has excellent fatigue properties, lubrication properties and electrical properties, and is used as a engineering resin in a wide range of fields, including automotive parts, electrical and electronic parts.

In recent years, the use of polyacetal resins has been attempted to be applied to exterior parts of automobiles, for example, surface decoration parts such as door handles, by utilizing the properties of polyacetal resins. Normal,
Thermosetting resin paints and thermoplastic resin paints are used as paints for surface decoration parts.

However, since these paints have poor surface activity of the polyacetal resin, they have low adhesion to the polyacetal resin and cannot be directly applied. For this reason, some attempts have been made to improve the adhesion as a paint.

For example, a method of pretreating with an acidic agent such as phosphoric acid or sulfuric acid (JP-A-55-92741, JP-A-57-96026),
Alternatively, a method using a primer obtained by dissolving a chlorinated polyolefin resin in a chlorine-containing solvent (Japanese Patent Application Laid-Open No. 59-91127) has been proposed.

(Problems to be Solved by the Invention) However, these conventional techniques include, for example, an increase in the number of steps such as acid treatment and washing with water, deformation of a material due to a drying step after coating, and toxicity of a chlorine-containing solvent. There was a problem and it was not a satisfactory method.

SUMMARY OF THE INVENTION An object of the present invention is to solve problems such as an increase in the number of steps, deformation of a material, and harmfulness of a solvent used in these conventional techniques. In other words, by applying a paint directly to the surface of the molded polyacetal product without pretreatment such as chemicals or primer treatment, and drying it, there is no deformation of the material, and a coated product with a coating layer with strong adhesion strength is applied. It is intended to simplify the process and reduce the production cost.

(Means for Solving the Problems) The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a molded article of a polyacetal resin composition comprising a polyoxymethylene, a polyacetal copolymer, and a polyvinyl polymer, and a synthetic resin The present inventors have found that the adhesion between the coating material and the paint is significantly improved, and have completed the present invention.

That is, the present invention provides: 1) (A) 100 parts by weight of polyoxymethylene, (B) polyoxymethylene and the general formula (I) (In the formula, R ₁ represents hydrogen or an alkyl group, R ₂ represents a group selected from a phenyl group, a cyano group, a chloro group, and an alkyl ester group. N is an integer of 1 or more.) 1 to 1,700 parts by weight of a polyacetal copolymer comprising a polymer having the following structure: (C) a general formula (II): (In the formula, R ₃ represents hydrogen or an alkyl group, and R ₄ represents a group selected from a phenyl group, a cyano group, a chloro group, and an alkyl ester group. N is an integer of 1 or more.) Polyvinyl polymer having a structure of from 0 to 1,200
A method for producing a polyacetal resin laminate, wherein a synthetic resin coating layer is formed on a polyacetal resin substrate obtained by molding a polyacetal resin composition containing: 2) a polymer having a structure represented by the general formula (I):
Styrene polymer, acrylonitrile polymer, vinyl chloride polymer, styrene / acrylonitrile copolymer, polymer of alkyl acrylate, polymer of alkyl methacrylate, copolymer of alkyl acrylate and styrene or acrylonitrile There is a characteristic in a certain point. 3) the polyvinyl polymer represented by the general formula (II) is a styrene polymer, an acrylonitrile polymer, a vinyl chloride polymer, a styrene / acrylonitrile copolymer, a polymer of an alkyl acrylate, an alkyl methacrylate; And a copolymer of alkyl acrylate and styrene or acrylonitrile. 4) It is also characterized in that the amount of the polyacetal copolymer (B) added is 200 to 1,500 parts by weight based on 100 parts by weight of polyoxymethylene. 5) It is also characterized in that the amount of the polyvinyl polymer (C) added is 0 to 500 parts by weight based on 100 parts by weight of the polyoxymethylene. 6) The synthetic resin coating layer is also characterized in that it is a thermosetting resin coating layer or a thermoplastic resin coating layer. Another feature is that 7) the thermosetting resin coating layer is formed using a thermosetting acrylic resin coating, a polyurethane resin coating, an epoxy resin coating, or an amino alkyd resin coating. 8) It is also characterized in that the thermoplastic resin coating layer is formed using an acrylic resin paint or a vinyl resin paint. 9) A method of forming a synthetic resin coating layer on a polyacetal resin substrate includes brush coating, dip coating, spray coating,
Another characteristic is that it is an electrostatic coating. 10) It is also characterized in that the thickness of the coating layer is 10 to 100 μm.

In the present invention, the polyacetal resin composition used as the polyacetal resin substrate includes: (A) 100 parts by weight of polyoxymethylene, (B) polyoxymethylene and a general formula: (In the formula, R ₁ represents hydrogen or an alkyl group, R ₂ represents a group selected from a phenyl group, a cyano group, a chloro group, and an alkyl ester group. N is an integer of 1 or more.) 1 to 1,700 parts by weight of a polyacetal copolymer comprising a polymer having the following structure: (C) a general formula (II): (In the formula, R ₃ represents hydrogen or an alkyl group, and R ₄ represents a group selected from a phenyl group, a cyano group, a chloro group, and an alkyl ester group. N is an integer of 1 or more.) Polyvinyl polymer having a structure of from 0 to 1,200
A polyacetal resin composition comprising:

 Hereinafter, the present invention will be described specifically.

The polyoxymethylene (A) used in the polyacetal resin composition includes two types, a homopolymer and a copolymer. The first group, homopolymers, are polymers obtained by homopolymerizing formaldehyde or trioxane. The copolymer belonging to the second group is a polymer obtained by copolymerizing formaldehyde or trioxane and a cyclic ether.

Examples of the cyclic ether constituting one component of the copolymer include an alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide; and a cyclic formal such as 1,4-butanediol formal, ethylene glycol formal and diethylene glycol formal.

The polyacetal copolymer (B) used in the polyacetal resin composition is composed of polyoxymethylene and a compound represented by the general formula (I): (In the formula, R ₁ represents hydrogen or an alkyl group, R ₂ represents a group selected from a phenyl group, a cyano group, a chloro group, and an alkyl ester group. N is an integer of 1 or more.) Block copolymer or graft copolymer comprising a polymer having the following structure:

There are two types of polyoxymethylene in the polyacetal copolymer (B), a homopolymer and a copolymer. The homopolymer is a polymer composed of repeating oxymethylene units and (—OCH ₂ ), and the copolymer is composed of the following oxyalkylene units in a chain composed of repeating oxymethylene units: (Wherein, R ₀ and R ₀ ′ are the same or different and each represent hydrogen, an alkyl group or an aryl group. M is an integer of 2 or more, and preferably m = 2 to 6.). It is a polymer having a modified structure.

The polyacetal copolymer (B) has, for example, the structure represented by the general formula (I) and homopolymerizes formaldehyde or trioxane in the presence of a polymer having a functional group, or forms formaldehyde or trioxane with It can be obtained by copolymerizing with a cyclic ether.

The number average molecular weight of the polyacetal copolymer (B) is 1
A range of 10,000 to 500,000 is preferred. Further, at least one functional group such as a hydroxyl group, an amino group, a carboxy group, an epoxy group, and an acid anhydride group is contained in a terminal or a chain of the polymer having a structure represented by the general formula (I). By polymerizing the above oxymethylene in the presence of the polymer, it is possible to adjust the molecular weight of the desired polyacetal copolymer.

Examples of the polymer having the structure represented by the general formula (I) include a styrene polymer, an acrylonitrile polymer,
Examples thereof include a vinyl chloride polymer, a styrene / acrylonitrile copolymer, a polymer of an alkyl acrylate, a polymer of an alkyl methacrylate, and a copolymer of an alkyl acrylate and styrene or acrylonitrile.

Examples of the alkyl ester of acrylic acid and methacrylic acid include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, octyl methacrylate,
Representative examples include hydroxyethyl methyl methacrylate.

Examples of the cyclic ether constituting one component of polyoxymethylene include alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide; and cyclic formals such as ethylene glycol formal, diethylene glycol formal and 1,4-butanediol formal.

Further, the polyvinyl polymer (C) used in the polyacetal resin composition has a general formula: (In the formula, R ₃ represents hydrogen or an alkyl group, and R ₄ represents a group selected from a phenyl group, a cyano group, a chloro group, and an alkyl ester group. N is an integer of 1 or more.) It is a polymer having the following structure.

Examples of the polymer (C) having a structure represented by the general formula (II) include a styrene polymer, an acrylonitrile polymer, a vinyl chloride polymer, a styrene / acrylonitrile copolymer, a polymer of an alkyl acrylate, Examples thereof include a polymer of an alkyl methacrylate and a copolymer of an alkyl acrylate and styrene or acrylonitrile.

Examples of the alkyl ester of acrylic acid and methacrylic acid include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, octyl methacrylate,
Representative examples include hydroxyethyl methyl methacrylate.

The amount of the polyacetal copolymer (B) needs to be between 1 and 1,700 parts by weight based on 100 parts by weight of the polyoxymethylene. When the addition amount is less than 1 part by weight,
The adhesion of the synthetic resin coating layer is poor, and a good polyacetal resin laminated structure cannot be obtained. This tendency becomes remarkable especially when the polyvinyl polymer is not added. On the other hand, when the addition amount exceeds 1,700 parts by weight, the mechanical properties which are characteristics of the polyacetal resin such as creep characteristics, fatigue characteristics and impact characteristics are greatly reduced. In this sense, the more preferable addition amount is 200 to 1,500 parts by weight.

Further, the amount of the polyvinyl polymer (C) needs to be between 0 and 1,200 parts by weight based on 100 parts by weight of the polyoxymethylene. If the amount exceeds 1,200 parts by weight, the mechanical properties which are characteristics of polyacetal, such as creep characteristics, fatigue characteristics and lubrication characteristics, are greatly reduced. The preferred amount is 0 to 500 parts by weight.

Polyacetal resin compositions can be used in common applications such as heat stabilizers, antioxidants, release agents, weathering agents, antistatic agents, coloring agents, reinforcing agents, surfactants, inorganic fillers, etc. Can be added.

The polyacetal resin substrate in the present invention is obtained by molding the polyacetal resin composition into a desired shape by a known molding method such as an injection molding method or an extrusion molding method.

The polyacetal resin laminated structure of the present invention is obtained by forming a synthetic resin coating layer on the polyacetal resin substrate thus obtained. Examples of the synthetic resin coating layer include a thermosetting resin coating layer and a thermoplastic resin coating layer.

The thermosetting resin coating layer is formed using a thermosetting resin coating. Typical examples of the thermosetting resin coating include a thermosetting acrylic resin coating, a polyurethane resin coating, an epoxy resin coating, and an amino alkyd. Resin paints and the like can be mentioned.

Examples of the thermosetting acrylic resin paint include a paint composed of a mixture of an acrylic resin obtained by copolymerizing an acrylic monomer having an active functional group and a crosslinking agent. Acrylic resin is, for example, acrylic acid; methyl acrylate;
Alkyl acrylates such as ethyl acrylate and butyl acrylate; methacrylic acid; methyl methacrylate;
Ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, acrylic monomers such as alkyl methacrylates such as lauryl methacrylate and hydroxyl alkyl methacrylate, acrylic acid, methacrylic acid, glycidyl methacrylate, methylol acrylamide, methylol methacrylamide It is a copolymer with an acrylic monomer having an active functional group such as an etherified product.

Amino resins, epoxy resins, carboxyl polymers, epoxyamino resins, and the like are used as the cross-linking agent, and an acid or chlorine is used as a catalyst as needed.

Examples of the polyurethane resin paint include a polyol-curable polyurethane resin paint. Examples of the polyol include a polyester polyol, an acrylic polyol, and a polyether polyol.

Polyester polyol is formed by the reaction of a dibasic organic acid and a glycol, and examples of the dibasic acid include adipic acid, sebacic acid, dimer acid, and phthalic anhydride. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylolpropane, glycerin and the like are used, respectively.

The acrylic polyol is a copolymer of an acrylic monomer having a hydroxyl group and an acrylate ester; examples of the acrylic monomer having a hydroxyl group include 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate;
Examples of the acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, and the like. Alternatively, styrene may be used.

The polyether polyol is obtained by reacting glycols with propylene oxide in the presence of an alkali catalyst. Examples of the glycols include propylene glycol, glycerin, trimethylolpropane, hexanetriol, sorbitol and the like.

Further, an isocyanate compound is used as a curing agent. As the isocyanate compound, compounds having two or more isocyanate groups, for example, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), meta-xylylene diisocyanate (MXDI), hexamethylene Diisocyanate (HDI), lysine diisocyanate (LD
I), hydrogenated HDI, hydrogenated TDI, isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), dimer acid diisocyanate (DDI) and the like are used.

Examples of the epoxy resin paint include a paint comprising a mixture of an epoxy resin having one or more epoxy groups in a polymer molecule and a curing agent. Epoxy resin may be modified with alkyd resin, polyethylene glycol, fatty acid, coal tar, diisopropanolamine, etc., as a curing agent, phenol resin,
Amino resins, melamine resins, isocyanates, amines (such as ethylenediamine and diethylenetriamine) are used.

Examples of the amino alkyd resin paint include a paint composed of a mixture of an alkyd resin and an amino resin.
Alkyd resins are, for example, maleic anhydride, phthalic anhydride, condensates of polyhydric carboxylic acids or anhydrides such as isophthalic acid and polyhydric alcohols such as glycerin and pentaerythritol or coconut oil, linseed oil Oil-modified alkyd resin modified with fatty acids such as castor oil, soybean oil, and tall oil. On the other hand, the amino resin is, for example, butoxymethylol urea or butoxymethylol melamine which is made oil-soluble by etherifying a condensate of urea or melamine and formaldehyde with an alcohol such as butanol.

The thermoplastic resin coating film layer is formed using a thermoplastic resin paint, and as a representative example thereof, an acrylic resin paint,
And vinyl resin paints.

Examples of the acrylic resin paint include a paint made of an acrylic resin obtained by homopolymerizing or copolymerizing an acrylic monomer. Examples of the acrylic monomer include acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, and the like.Examples of the acrylic acid ester include methyl acrylate, ethyl acrylate,
Examples include butyl acrylate and the like. Examples of the methacrylate include methyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate,
Lauryl methacrylate, hydroxyalkyl methacrylate and the like can be mentioned. If necessary, celluloses such as nitrocellulose, ethylcellulose, acetylcellulose and acetylbutylcellulose are added to the acrylic resin.

Examples of the vinyl resin paint include homopolymers or copolymers of vinyl monomers such as vinyl chloride, vinylidene chloride, vinyl alcohol, vinyl esters, and unsaturated dibasic acids, and the above-mentioned vinyl monomers and acrylic acid or acrylic acid esters. It is a paint made of a copolymer with an acrylic monomer such as Vinyl esters include vinyl acetate, vinyl propionate, vinyl crotonic acid, vinyl caproate, vinyl laurate, vinyl stearate, and the like; unsaturated dibasic acids include maleic acid, fumaric acid, crotonic acid, itacone Acids and the like. Also,
Acrylic monomers include, for example, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, etc .; Acrylic esters include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, etc .; methacrylic acid Examples of the ester include methyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, and hydroxyalkyl methacrylate. Further, styrene or butadiene may be used instead of the acrylic monomer. Further, if necessary, the homopolymer and the copolymer of the vinyl monomer may be subjected to saponification or acetalization.

In the present invention, in order to form a synthetic resin coating layer on the polyacetal resin substrate, a commonly used coating method such as brush coating, dip coating, spray coating, and electrostatic coating is used.

Further, the thickness of the coating layer in the present invention is determined by the desired physical properties of the laminated structure, and is not particularly limited,
Preferably it is 10 to 100 μm.

(Examples) Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

In addition, the characteristic value in an Example was measured by the following method.

(1) MI; measured according to ASTM D-1238E conditions. It is a measure of molecular weight.

(2) Adhesion: A 1 mm square test was conducted according to JIS K 5400-1979, and the number of squares that did not peel off was measured.

(3) IZOD impact value (with notch): Measured according to ASTM D-256. It is a measure of mechanical properties.

Example 1 (1) Production of a polyacetal resin substrate.

Polyoxymethylene: Formaldehyde was homopolymerized using dibutyltin dimethoxide (anionic polymerization catalyst) as a catalyst, and the terminal was stabilized with acetic anhydride. The MI of this polymer is 8.7 g / 10
Minutes.

Polyacetal copolymer: Dibutyltin dimethoxide was added as a polymerization catalyst to toluene containing polyisobutyl methacrylate (MnOH11,000) having a terminal —OH group, and then formaldehyde was added. After a predetermined time, toluene and the polymer were separated, and the polymer was stabilized with acetic anhydride. Of this polymer
The MI was 3.4 g / 10 minutes.

Polyvinyl polymer: Isobutyl methacrylate was polymerized using AIBN (radical polymerization catalyst) to obtain a polymer having a weight average molecular weight of 110,000.

Mixing: polyoxymethylene 100 parts by weight Polyacetal copolymer 150 parts by weight Polyvinyl polymer 50 parts by weight Heat stabilizer Nylon 66 0.5 parts by weight Antioxidant [2,2-methylenebis (4-methyl-6-t)
-Butylphenol), hereinafter abbreviated as AO] 0.4 part by weight, and then melted with a 30 mmφ twin screw extruder to obtain a polyacetal resin composition.

Polyacetal resin substrate: The polyacetal resin composition was injection-molded to prepare a flat plate (length: 120 mm, width: 80 mm, thickness: 3 mm) to obtain a polyacetal resin substrate.

(2) Production of a polyacetal resin laminated structure and measurement of physical properties.

A laminated structure was manufactured on the flat plate obtained in (1) by the following paint and processing method.

Amino alkyd resin paint [Kansai Paint Co., Ltd., Amirac No.1000, White No.531, diluted with special thinner (50%)]
After standing for 30 minutes, the mixture was cured by heating at 140 ° C. for 30 minutes to obtain a laminated structure. This had a coating thickness of about 53 μm.

Epoxy resin paint [Plavest EX No.30, red, diluted with dedicated thinner (50
%)] By air spray coating and leave it at room temperature for 20 minutes.
Heating and curing at 40 ° C for 40 minutes, a laminated structure was obtained. This had a coating thickness of about 41 μm.

Acrylic resin paint [Plavest ST No.20, red, manufactured by Takashi Kubo Paint Co., Ltd., diluted with special thinner (50
%)] By air spray coating, and after painting,
After heating and drying for a minute, a laminated structure was obtained. This had a coating thickness of about 63 μm.

Thermosetting acrylic resin paint [Plavest EX No.90, black, diluted with special thinner (5
0%)] by air spraying and leave at room temperature for 30 minutes.
It was cured by heating at 0 ° C. for 30 minutes to obtain a laminated structure. This had a coating thickness of 38 μm.

Urethane resin paint [Puravest ST 700, black, diluted with special thinner (50%) manufactured by Takashi Kubo Paint Co., Ltd.]
Air spray painted, leave at room temperature for 10 minutes, then
And heat-cured for a minute to obtain a laminated structure. This had a coating thickness of about 67 μm.

A vinyl resin paint [manufactured by Kansai Paint Co., Ltd., Vinybon 100, white, diluted with a special thinner (60%)] was applied by air spray, and left at room temperature for 24 hours to obtain a laminated structure. This had a coating thickness of about 59 μm.

Table 2 shows the measurement results of the mechanical properties and the adhesion of the obtained laminated structure.

As shown in Table 2, the polyacetal resin laminated structure showed excellent adhesion in any of the paints. Moreover, it had excellent mechanical properties as a polyacetal resin structure.

Example 2 (1) Production of a polyacetal resin substrate.

Polyoxymethylene; Trioxane and ethylene oxide are copolymerized using boron trifluoride (cationic polymerization catalyst) as a catalyst, and the polymer is stabilized by melt hydrolysis using triethylamine-water in an extractor. Was. The MI of this polymer was 18 g / 10 minutes.

Polyacetal copolymer: In toluene containing a methyl methacrylate / n-butyl methacrylate copolymer having an OH group at the terminal (Mn = 18,000), tetraoctylammonium acetate (anionic polymerization catalyst) is added as a polymerization catalyst, and then formaldehyde is added. Was added. After a predetermined time, toluene and the polymer were separated, and then the polymer was stabilized with acetic anhydride. The MI of this polymer was 1.4 g / 10 minutes.

Polyvinyl copolymer: A polymer having a weight average molecular weight of 160,000 was obtained by polymerizing methyl methacrylate and n-butyl methacrylate using AIBN (radical polymerization catalyst).

Mixing: 100 parts by weight of polyoxymethylene 250 parts by weight of polyacetal copolymer 50 parts by weight of polyvinyl polymer 0.5 part by weight of nylon 66 0.4 part by weight of AO were mixed and then melted by a 65 mmφ twin screw extruder to obtain a polyacetal resin composition. Obtained.

Polyacetal resin substrate: The polyacetal resin composition was injection-molded to prepare a flat plate (length: 120 mm, width: 80 mm, thickness: 3 mm) to obtain a polyacetal resin substrate.

(2) Production of a polyacetal resin laminated structure and measurement of physical properties.

A laminated structure was manufactured on the flat plate obtained in (1) using the paint shown in Example 1 and the same treatment method.

Table 2 shows the measurement results of the mechanical properties and the adhesion of the obtained laminated structure.

As shown in Table 2, the polyacetal resin laminated structure showed excellent adhesion in any of the paints. Moreover, it had excellent mechanical properties as a polyacetal resin laminated structure.

Examples 3 to 14 (1) Production of polyacetal resin substrate.

Polyoxymethylene: Formaldehyde was homopolymerized using dimethyl distearyl ammonium propionate (anionic polymerization catalyst) as a catalyst, and the terminal was stabilized with acetic anhydride.
The MI of this polymer was 27 g / 10 minutes.

Polyacetal copolymer: Dibutyltin dimethoxide was added as a polymerization catalyst to toluene containing a polymer having a functional group at a terminal or chain shown in Table 1 at a predetermined concentration, and then formaldehyde was added. After a predetermined time, toluene and the polymer were separated, and the polymer was stabilized with acetic anhydride to obtain a polyacetal copolymer (Table 1 shows the MI of the polyacetal copolymer).

Polyvinyl polymer: The vinyl monomers shown in Table 1 were homopolymerized or copolymerized using benzoyl peroxide or AIBN to obtain a polyvinyl polymer.

Mixing: To 100 parts by weight of polyoxymethylene, polyacetal copolymer and polyvinyl polymer were added in the amounts shown in Table 1, and 0.35 parts by weight of nylon 66 and 0.4 part by weight of antioxidant AO were added. And melt-mixed with a 30 mmφ twin screw extruder to obtain 12 types of polyacetal resin compositions.

Polyacetal resin substrate: The obtained polyacetal resin composition was injection-molded to prepare a flat plate (length 120 mm, width 80 mm, thickness 3 mm) to obtain 12 types of polyacetal resin substrates.

(2) Production of a polyacetal resin laminated structure and measurement of physical properties.

The same operation as in Example 1 was performed on the 12 types of flat plates obtained in (1) using the paint shown in Example 1 to produce a polyacetal resin laminated structure. Mechanical properties of these laminated structures,
Table 2 shows the measurement results of the adhesiveness.

As shown in Table 2, it was proved that all the polyacetal resin laminated structures had excellent adhesion. These laminated structures also have excellent mechanical properties.

Examples 15 to 17 (1) Production of polyacetal resin substrate.

 Polyoxymethylene: The polymer produced in Example 1 was used.

Polyacetal copolymer: A polymer having a functional group in a terminal or a chain shown in Table 1 was charged into trioxane containing ethylene oxide, and then boron trifluoride dibutyl etherate was added as a polymerization catalyst and reacted for a predetermined time. A polyacetal copolymer was obtained.

Polyvinyl polymer: The vinyl monomers shown in Table 1 were homopolymerized or copolymerized using benzoyl peroxide or AIBN to obtain a polyvinyl polymer.

Mixing: To 100 parts by weight of polyoxymethylene, the polyacetal copolymer and the polyvinyl polymer were added in the amounts shown in Table 1, and 0.45 parts by weight of nylon 66 and 0.4 part by weight of antioxidant AO were added. And a 30 mmφ twin screw extruder to obtain three types of polyacetal resin compositions.

Polyacetal resin substrate: The obtained polyacetal resin composition was injection-molded to prepare a flat plate (length 120 mm, width 80 mm, thickness 3 mm) to obtain three types of polyacetal resin substrates.

(2) Production of a polyacetal resin laminated structure and measurement of physical properties.

The same operation as in Example 1 was performed on the three types of flat plates obtained in (1) using the paint shown in Example 1 to produce a polyacetal resin laminated structure.

Table 2 shows the measurement results of mechanical properties and adhesion of these laminated structures.

As shown in Table 2, all of the polyacetal resin laminated structures exhibited excellent adhesion. These laminated structures also have excellent mechanical properties.

Comparative Example 1 To 100 parts by weight of the polyoxymethylene of Example 3, 0.5 part by weight of nylon 66 and 0.4 part by weight of AO were added and melt-mixed with a 30 mmφ twin screw extruder. Example 1 using this polymer
A flat plate was prepared by the same operation as described above, and a laminated structure was prepared using the paint and processing method shown in Example 1. Table 2 shows the adhesion of the obtained laminated structure.

As shown in Table 2, the adhesion of the laminated structure was extremely poor.

Comparative Examples 2-3 A polyacetal copolymer was synthesized from an acrylonitrile / styrene copolymer having an -OH group at a terminal and formaldehyde. This polyacetal copolymer was added to 100 parts by weight of the polyoxymethylene of Example 1 in the amounts shown in Table 1, and 0.5 part by weight of nylon 66 and 0.4 part by weight of AO were added, followed by melting with a 30 mmφ twin screw extruder. The mixture was mixed to obtain a polyacetal resin composition.

Using the obtained polyacetal resin composition, a flat plate was prepared by the same operation as in Example 1, and a polyacetal resin laminated structure was manufactured by the coating material and the treatment method shown in Example 1. Table 2 shows the adhesiveness and mechanical properties of the laminated structure.

The polyacetal resin laminated structure of Comparative Example 2 in which the addition amount of the polyacetal copolymer was excessive was poor in mechanical properties. On the other hand, the adhesion of the polyacetal resin laminated structure of Comparative Example 3 in which the amount of the polyacetal copolymer added was too small was poor.

Comparative Example 4 100 parts by weight of the polyoxymethylene of Example 3, Comparative Example 2
200 parts by weight of the polyacetal copolymer used in Example 1 and a polyvinyl polymer 1300 synthesized from acrylonitrile and styrene
Parts by weight, nylon 66 0.5 parts by weight, and AO 0.4 parts by weight were mixed and melt-mixed with a 30 mmφ twin screw extruder to obtain a polyacetal resin composition. Using this composition, a flat plate was prepared by the same operation as in Example 1, and a polyacetal resin laminated structure was produced by the coating and processing method shown in Example 1. Table 2 shows the adhesiveness and mechanical properties of the laminated structure.

It can be seen that when the amount of the polyvinyl polymer added was excessive, the mechanical properties of the laminated structure were significantly reduced.

(Effects of the Invention) As described above, in the present invention, on a composition substrate in which a specific amount of a specific polyacetal copolymer (B) and a specific amount of a polyvinyl copolymer (C) are blended with polyoxymethylene (A), Since the synthetic resin coating layer is formed, the adhesion between the two can be significantly improved without a pretreatment step such as a special chemical treatment or a primer treatment.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 27:06) (C08L 59/04 33:04) (C08L 59/04 33:20)

Claims (10)

(57) [Claims] 1. A polyoxymethylene (A) 100 parts by weight, (B) polyoxymethylene and a compound of the formula (I) (In the formula, R ₁ represents hydrogen or an alkyl group, R ₂ represents a group selected from a phenyl group, a cyano group, a chloro group, and an alkyl ester group. N is an integer of 1 or more.) 1 to 1,700 parts by weight of a polyacetal copolymer comprising a polymer having the following structure: (C) a general formula (II): (In the formula, R ₃ represents hydrogen or an alkyl group, and R ₄ represents a group selected from a phenyl group, a cyano group, a chloro group, and an alkyl ester group. N is an integer of 1 or more.) A polyacetal resin, comprising a polyacetal resin substrate obtained by molding a polyacetal resin composition containing 0 to 1,200 parts by weight of a polyvinyl polymer having a structure of Manufacturing method of laminate. 2. A polymer having a structure represented by the general formula (I) is a styrene polymer, an acrylonitrile polymer, a vinyl chloride polymer, a styrene / acrylonitrile copolymer,
The method for producing a polyacetal resin laminate according to claim 1, wherein the polyacetal resin laminate is a polymer of an alkyl acrylate, a polymer of an alkyl methacrylate, or a copolymer of an alkyl acrylate and styrene or acrylonitrile. 3. The polyvinyl polymer represented by the general formula (II) is a styrene polymer, an acrylonitrile polymer, a vinyl chloride polymer, a styrene / acrylonitrile copolymer, a polymer of an alkyl acrylate, an alkyl methacrylate. 3. The method for producing a polyacetal resin laminate according to claim 1, wherein the polyacetal resin laminate is an ester polymer or a copolymer of an alkyl acrylate and styrene or acrylonitrile. 4. The polyacetal copolymer (B) is added in an amount of 200 to 1,500 based on 100 parts by weight of polyoxymethylene.
The method for producing a polyacetal resin laminate according to any one of claims 1 to 3, wherein the amount is parts by weight. 5. The polyacetal according to claim 1, wherein the amount of the polyvinyl polymer (C) is 0 to 500 parts by weight based on 100 parts by weight of the polyoxymethylene. Manufacturing method of resin laminate. 6. The synthetic resin coating layer is a thermosetting resin coating layer or a thermoplastic resin coating layer.
5. The method for producing a polyacetal resin laminate according to any one of 5. 7. A thermosetting resin coating film layer comprising a thermosetting acrylic resin coating, a polyurethane resin coating, an epoxy resin coating,
The method for producing a polyacetal resin laminate according to claim 6, wherein the polyacetal resin laminate is formed using an amino alkyd resin paint. 8. The method for producing a polyacetal resin laminate according to claim 6, wherein the thermoplastic resin coating layer is formed using an acrylic resin paint or a vinyl resin paint. 9. The method for forming a synthetic resin coating layer on a polyacetal resin substrate by brush coating, dip coating, spray coating or electrostatic coating.
The method for producing a polyacetal resin laminate according to any one of the above. 10. The method for producing a polyacetal resin laminate according to claim 1, wherein the thickness of the coating layer is 10 to 100 μm.