JPH02153721A - Method for molding and manufacturing compound molded plate - Google Patents

Abstract

PURPOSE:To obtain a molding and manufacturing method being cheap in its manufacturing cost and excellent in its workability of the process by using water formable polyisocyanate resin as the binding agent of a base material or the like upon molding and manufacturing a compound molded plate by the use of a surface material, backing material, core layer material, and rear surface material. CONSTITUTION:A liquid infiltration base material to be a core layer material is left as being sprayed with water, following this, the rear surface of a surface material to be a back and front part is uniformly applied with water foamable polyisocyanate resin by means of a spray or the like. The spraying rate of the water foamable polyisocyanate resin is decided in consideration of foaming rate or an infiltrating property or the like to the core layer material. After spraying resin, the lamination is performed to be for example a surface material / backing material / core layer material / backing material / rear surface material, and then it may be set within a mold having a desired configuration, thereby obtaining a compound molded plate by the press. The molding temperature is usually at 50 - 80 deg.C, and the time required for the press is usually for 2 - 5 minutes, and preferably, the pressing pressure may be of the type which can tolerate the foaming pressure of the resin. Thus, an article having a free curved surface can be molded by the use of a mold, and by an internal die press mold upon pressing it.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming and manufacturing a composite molded plate.

More specifically, from the reaction of an organic polyisocyanate compound containing two or more isocyanate groups in the molecule and/or its isocyanate group-terminated prepolymer with one or more polyoxyalkylene-added higher aliphatic amine derivatives. The present invention relates to a method for molding and manufacturing a composite molded plate using the resulting water-foamable polyisocyanate resin as a binder for base materials.

[Conventional technology]

Many documents have been published and have been put into practical use regarding forming and manufacturing techniques for composite molded plates having a multilayer structure.

For example, (1) STRATOTEC system, (2) GLOBAL system,
(3) Elastoflex (F, LASTPLEX) system, (4) ROTHFRERH system, etc., but each system has advantages and disadvantages in terms of manufacturing cost, process workability, cycle time, product properties, etc. have.

Listing the disadvantages of each of the above systems, the following can be considered.

Regarding (1), press molding is performed after spraying urethane foam liquid and glass fiber as the core layer material, but it is difficult to obtain uniformity in the application of glass fiber, and the rise of the urethane foam is also uneven. This has the disadvantage that the defect rate is high as a result. Moreover, the equipment cost is not cheap either.

Regarding (2), what is considered to be the biggest manufacturing drawback is that organic solvents are used in the process of impregnating the urethane foam with resin, which poses a major problem in terms of the working environment.

Regarding (3), hot forming (TH6RMOFOAMIN)
G) method has the drawbacks of high energy cost and long cycle time.

Regarding (4), there is a large loss during molding, which results in an increase in costs, and furthermore, a large burden on equipment costs.

As described above, all systems have their own drawbacks, and although these systems have been put into practical use, there is still a need for a molding method using a processing method using an improved resin system. ing.

[Problem to be solved by the invention]

The purpose of the present invention is to eliminate the drawbacks of conventional molding and manufacturing technology for composite molded plates having a multilayer structure, and to achieve low manufacturing costs, excellent process workability, and shortened cycle time. Another object of the present invention is to provide a method for molding and manufacturing a composite molded plate with a low defect rate and without using organic solvents.

As a result of extensive research and consideration, the present inventors have discovered that organic polyisocyanate compounds and/or isocyanate group-terminated prepolymers are used as binders for various base materials when producing composite molded plates having a multilayer structure. By using a water-foamable polyisocyanate resin obtained by modification with an additional higher aliphatic amine derivative, there is no need to add an organic solvent, it has excellent workability and dispersibility in water, and can be made into a foamable resin at will. Since the speed can be adjusted and the foamed resin can be arbitrarily controlled from elastic and soft to rigid and rigid, it can be Furthermore, the inventors have discovered that various board properties can be imparted to composite molded boards by adjusting the amount of water-foamable polyisocyanate resin applied, that is, the amount of resin impregnated into the core material, and have completed the present invention.

[Means for solving problems]

That is, in the present invention, when molding and manufacturing a composite molded plate using a surface material, a backing material, a core layer material, and a back material,
This is a method for molding and manufacturing a composite molded plate, characterized in that a water-foamable polyisocyanate resin is used as a binder for the above-mentioned base materials.

Substrates that can be used in the present invention include colored PVC sheets treated with embossing, matting, etc. as surface materials;
Plastic sheets made of chemically treated polyurethane resins, natural rubber, AS resins, etc. or polyblends, colored woven fabrics made of glass fibers, cotton, wool, chemical fibers, etc. Also includes those with back side treatment such as polyethylene coating.

Backing materials include glass fibers, glass fiber mats, propylene fibers, rock wool, palm rock slice chips, and other fillers.

The core layer material is not particularly limited as long as it has the property of being impregnated with the foamed resin to maintain the shape of the molded plate after the water-foamable polyisocyanate resin is foamed through the backing material, but typical base materials may be used. Examples of the material include open-cell plastic foam, corrugated paper, and textile scraps.

Examples of the back surface material include plastic sheets, paper such as Japanese paper, cloth such as cheesecloth and nonwoven fabric, and also includes those whose back surface has been treated in the same manner as the surface material.

The water-foamable polyisocyanate resin that can be used in the present invention is an organic polyisocyanate compound containing two or more isocyanate groups in the molecule and/or isocyanate group-terminated prepolymer, monoalkoxylate dialkylamine, dialkoxylate mono It is obtained by reaction with one or more polyoxyalkylene-adducted higher aliphatic amine derivatives typified by alkylamines, trialkoxylate monoalkyldiamines, dialkoxylate monoalkylamides, and trialkoxylate monoalkylamide amines.

Examples of organic polyisocyanate compounds for the resin include tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, biphenylene diisocyanate, diphenyl ether diisocyanate, tolydine diisocyanate, and hexane diisocyanate having two or more functional groups. Examples include methylene diisocyanate and isophorone diisocyanate, and also include derivatives of these isocyanates and compounds similar to these, either singly or in mixtures of two or more.

Further, the isocyanate group-terminated prepolymer can be obtained by reacting an organic polyisocyanate compound with a polyol having active hydrogen.

As polyols having active hydrogen, all polyols having at least two or more hydroxyl groups in one molecule can be used, but typical examples include polyester polyols, polyether polyols, epoxy polyols, etc. A combination of two or more polyols can also be used.

Examples of polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, glycerin, and trimethylolpropane. , pentaerythritol, sorbitol, etc., and one or more compounds having at least two hydroxyl groups, such as malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, sebacic acid, oxalic acid, phthalic acid, and terephthalic acid. , azelaic acid, trimellitic acid, etc.
It can be produced by a known method using one or more compounds having one or more carboxyl groups. Also included are lactone-based polyesters obtained by ring-opening polymerization of monomers having a lactone ring, such as ε-caprolactone and δ-no(rerolactone).

Examples of polyether polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, glycerin, sorbitol, shake rose, bisphenol A1 pentaerythritol, and the like. alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. having 2 or more carbon atoms, using one or more compounds having at least two active hydrogens as a polyol starting compound;
It is produced by addition polymerizing one or more monomers such as epichlorohydrin by a known method.

In addition, these active hydrogen-containing polyols have the general formula R
Also included are alkoxy polyalkylene glycols having a molecular weight of 250 to 4000 and represented by 30-fRaO 11 (R,: alkyl group, R4: alkylene group).

The polyoxyalkylene-added higher aliphatic amine derivatives used in the present invention are represented by -m formulas (1), (2), (3) and (4).

R2: linear or branched alkyl group or hydroxyalkyl group having an average carbon number of 7 to 39 (however, alkenyl group, hydroxyalkenyl group, phenyl group, benzyl group, and those having an ether bond in the carbon chain are also included) X++Xz+ )'t+3'g+3'3+Z++Zz
: An integer from 1 to 350 In the formula, R: a linear or branched alkyl group or hydroxyalkyl group having an average carbon number of 8 to 40 (however, an alkenyl group, a hydroxyalkenyl group, a phenyl group, a benzyl group, and an ether bond in the carbon chain) R1: hydrogen or methyl group (however, hydrogen and methyl groups may be introduced in a random or block combination) n: an integer of 2 or 3.

It may be.

Examples of natural vegetable fatty acid residues include corn oil, cottonseed oil, peanut oil, rapeseed oil, sesame oil, soybean oil, safflower oil, coconut oil, palm oil, and palm kernel oil.

Examples of animal products include pork oil, beef tallow oil, whale oil, herring oil, squid oil, sardine whale oil, and whale oil. Oxygen-containing fatty acid residues can be obtained from cork oak bark oil and the like.

Currently, industrial methods for synthesizing fatty acids using petroleum as raw materials include liquid phase air oxidation of paraffins, hydroformylation of olefins (oxy method), and carbonylation (Koch method), and large-scale production is currently underway. There is.

These fatty acid residues from animal and vegetable oils or synthetic fatty acids may be used alone or in combination of two or more.

When molding and manufacturing the composite molded plate of the present invention, inorganic compounds,
A reinforcing agent, extender, flame retardant, etc. for synthetic resins such as organic compounds may be added to the water-foamable polyisocyanate resin.

For example, inorganic fillers include mica powder, powdered clay,
Examples include silica gel, limestone wax, potassium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, sodium silicate, silica sand, perlite, shirasu balloon, glass balloon, and the like.

Flame retardants include halogen organic phosphate compounds such as tris(chloroethyl) phosphate, tris(chlorpropyl) phosphate, tris(dichloropropyl) phosphate, tris(dibromopropyl) phosphate, and decabromodiphenyl oxide. There are halogen-based flame retardants such as Further, these inorganic and organic additives may be used alone or in combination of two or more.

The water-foamable polyisocyanate resin used in the present invention is a hydrophilic polyisocyanate resin composition with a relatively low viscosity. For this reason, the resin composition of the present invention does not particularly require a viscosity modifier, but it may be added or blended depending on the case. However, organic solvents with low boiling points such as acetic acid esters and ketones are undesirable due to the deterioration of the working environment and the risk of ignition, while alkylene carbonates and phthalic acid esters have high boiling and flash points. , is preferable as a viscosity modifier.

Foams having various properties can be obtained from the water-foamable polyisocyanate resin used in the present invention.

That is, the type of organic polyisocyanate compound may be changed, the organic polyisocyanate compound may be directly modified with a polyoxyalkylene-added higher aliphatic amine derivative, which is a compound in the present invention, or a general-purpose polyether polyol, By changing the type of modifier for producing prepolymers such as polyester polyols and the structure and molecular weight of polyoxyalkylene-added higher aliphatic amine derivatives, it is possible to change from soft foams with elasticity to hard foams with rigidity. Since the foaming ratio can be adjusted arbitrarily from several times to several tens of times, it has become possible to provide the composite molded plate with characteristics suitable for its intended use.

In addition, although the water-foamable polyisocyanate resin of the present invention has extremely high reactivity with water, it has excellent storage stability in a moisture-blocked system, shows almost no change in viscosity over time, and is stable even after long-term storage. It is also fully usable.

The molding and manufacturing of the composite molded plate of the present invention can be accomplished in the following manner.

Spray water on the liquid-impregnable base material that will be the core layer material in advance, then spray water-foamable polyisocyanate resin on the back side of the surface material that will become the front side, apply with a brush, use a doctor knife, roller, etc. Apply evenly using. Alternatively, the water-foamable polyisocyanate resin may be mixed with water and applied as an emulsion to the surface material or the core layer material. The coating amount of the water-foamable polyisocyanate resin is usually in the range of 100 to 5'OOg/4, and is determined by taking into consideration the amount of foaming, impregnation into the core layer material, and the like. After applying the resin, the composite molded plate is obtained by laminating, for example, surface material/backing material/core layer material/backing material/back material, setting it in a mold having a desired shape, and pressing. I can do it. A maximum mold temperature of 100°C is sufficient, and usually 50 to 80°C.
The pressing time is usually 1 minute or more and 2 to 5 minutes. The press pressure may be any pressure that can withstand the foaming pressure of the resin. When pressing, a mold is used to perform in-mold press molding, thereby making it possible to mold a product having a free-form surface.

The composite molded plate produced using the water-foamable polyisocyanate resin of the present invention as a binder is characterized by the type of resin, the type of base material, the amount of resin applied, the laminated thickness of the base material, and the molding after pressing. It is possible to change the hardness, elasticity, feel, and bond physical properties of the molded plate by adjusting the thickness of the plate, that is, the back ratio, etc., so it can be applied to an extremely wide range of fields.

For example, it can be applied to automobile interior materials (ceiling materials, seat wall surface materials, etc.), furniture materials, etc.

The composite molded plate of the present invention has many advantages in the manufacturing process, such as being able to be molded in a short time at low temperatures, not using low-boiling point solvents, and having a low defect rate because it is easy to obtain uniformity in the molded plate. However, the characteristic advantages of the molded plate itself include being lightweight, having excellent sound absorption properties, excellent heat resistance, and excellent heat insulation properties.

〔Example〕

The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

The polyoxyalkylene-adducted higher aliphatic amine derivative used in the examples is abbreviated as amine derivative polyol. Unless otherwise specified, parts and percentages in Examples and Comparative Examples are "parts by weight" and "% by weight," respectively.
shows.

Example 1 A water-foamable polyisocyanate resin (1) was prepared according to the following requirements.

Polyphenylmethane polyisocyanate (manufactured by Nippon Polyurethane Industries, Millionate MR-300, NGO content 3
1.5%) and 30 parts of methoxypolyethylene glycol having an average molecular weight of 700 were reacted at 80°C for 3 hours to obtain a self-emulsifying polyisocyanate resin.

After cooling this resin to 40°C or less, sardine oil amine E was added to it as an amine derivative polyol (corresponding to general formula 1).
15 (Alkyl distribution: approximately 90% carbon number 20-22, number of moles of ethylene oxide added is 15, hydroxyl value 143)
A water-foamable polyisocyanate resin was obtained by adding 238 parts while checking the temperature rise, and finally maintaining the temperature at 80°C for 3 hours. The NGO content of this resin is 22.0%
Met.

Example 2 A water-foamable polyisocyanate resin (II) was prepared in the following manner.

Liquid diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industries, Millionate MTL, NCO content 29.
0%) and 312 parts of a polyalkylene tetraol having an average molecular weight of 8,400, which is obtained by randomly polymerizing pentaerythritol with 80 parts of ethylene oxide and 20 parts of propylene oxide, were reacted at 80°C for 3 hours to form a hydrophilic polyisocyanate. Resin was obtained.

After cooling 1,000 parts of this resin to 40°C or less, it was added as an amine derivative polyol (corresponding to general formula 2) to tallow diamine E3 (alkyl distribution: 24% carbon atoms with 18 carbon atoms and carbon atoms with one unsaturated bond). 62 parts of 37% carbon number 18, 30% carbon number 16, 3 moles of ethylene oxide added, and hydroxyl value 390 were reacted in the same manner as in Example 1 to obtain a water-foamable polyisocyanate resin.

The NGO content of this resin was 19%.

Example 3 Water-foamable polyisocyanate resin (I[[)
was prepared.

To 1000 parts of self-emulsifying polyphenylmethane polyisocyanate (manufactured by Nippon Polyurethane Industries, Coronate 3053, NGO content 29.5%), beef tallow amide amine E15 was added as an amine derivative polyol (corresponding to general formula 4).
(Alkyl distribution: 24% 18 carbon atoms, 37% 18 carbon atoms with one unsaturated bond, 30% 16 carbon atoms, 15 moles of ethylene oxide added, hydroxyl value 190)
174.5 parts were reacted in the same manner as in Example 1 to obtain a water-foamable polyisocyanate resin. NC of this resin
The O content was 23%.

Example 4 A water-foamable polyisocyanate resin (IV) was prepared in the following process.

Polyphenylmethane polyisocyanate (manufactured by Nippon Polyurethane Industries, Millionate MR-100, NGO content 3
1.0%> Too portion was reacted with 157 parts of the amine derivative polyol used in Example 1 in the same manner as in Example 1 to obtain a water-foamable polyisocyanate resin. The NCO content of this resin was 25.0%.

Example 5 Using the resins prepared in Examples 1 to 4, composite molded plates were manufactured by combining various base materials.

Embossed non-stick colored PVC sheet treated with hot-melt polyethylene film as surface material, 230g/as backing material
A composite molded board was manufactured using a chopped glass fiber strand mat of Iil, a 5 m+m thick flexible polyurethane foam as the core layer material, and a nonwoven fabric treated in the same manner as the surface material as the back material. As a binder, the water-foamable polyisocyanate resin (1) prepared in Example 1 was used in various coating amounts. The resin was applied uniformly onto the polyethylene film of the front and back surfaces using a roller, and the core layer material was coated with 50% water to improve foaming properties.
g/+j spray applied. Pressing conditions are press temperature 7
0°C, press time 3 minutes and press pressure 10 kg/
It was c+il. The thickness of the molded plate was set to 5 mm using a spacer.

Table 1 shows the characteristics of the composite molded plate when the amount of resin applied was varied.

(Note 1) Table 1: Degree of warping in the longitudinal center of a test piece (length 250 mIlli 50 mm) Example 6 Using the same base material as in Example 5, using the binder as Example 2
A composite molded plate was manufactured using the water-foamable polyisocyanate resin (II) prepared in . The manufacturing conditions were the same as in Example 5, and the amount of resin applied was 148 g/rrf on the surface material.
The back material had a weight of 128 g/i. The properties of this composite molded plate are shown in Table 2.

Example 7 The same base material as in Example 5 was used except that a colored woven fabric treated with a hot-melt polyethylene film was used as the surface material,
A composite molded plate was manufactured using the water-foamable polyisocyanate resin (I[I) prepared in Example 3 as a binder. The manufacturing conditions were the same as Example 5 except that the press temperature was 80°C.
Same as above, the amount of resin applied is 124g/rrf on the surface material,
It was 104g/rrr for the back material. The properties of this composite molded plate are shown in Table 2.

Example 8 A composite molded board was manufactured using the same base material and binder as in Example 7. The binder was mixed with water in a ratio of 1:1 and sprayed as a water emulsion onto both sides of the flexible polyurethane foam as the core layer material. The amount of resin impregnated was 187 g/rrf. Since a large amount of water was impregnated into the flexible polyurethane foam, the pressing temperature was set to 100''C and the pressing time was set to 4 minutes.

The properties of this composite molded plate are shown in Table 2.

Example 9 A composite molded plate was manufactured using the same base material as in Example 7 and the water-foamable polyisocyanate resin (IV) prepared in Example 4. The manufacturing conditions were a press temperature of 70°C, a press time of 3 minutes, a press pressure of 10 kg/cd, and the amount of resin applied to the surface material was 128 g/n? , 102g/rr for back material
? Met. The properties of this composite molded plate are shown in Table 2.

Example 10 A water-foamable polyisocyanate resin (Vl) was prepared in the following manner.

To 1000 parts of self-emulsifying polyphenylmethane polyisocyanate (manufactured by Nippon Polyurethane Industries, Coronate 3053, NCO content 29.5%), as an amine derivative polyol (corresponding to general formula 3), hardened tallow amide E50 (
Alkyl distribution: 63% with 18 carbon atoms, 30 with 16 carbon atoms
%, number of moles of ethylene oxide added 50, hydroxyl value 48
) 199 parts were reacted in the same manner as in Example 1 to obtain a water-foamable polyisocyanate resin.

The NCO content of this resin was 24%.

Manufacture of composite molded plate The same base material as in Example 5 was used, and Example 1 was used as the binder.
Water-foamable polyisocyanate resin (Vl) prepared in 0
A composite molded plate was manufactured using The manufacturing conditions are as in Example 5.
Same as above, the amount of resin applied is 135g/rrr on the surface material,
! ! The surface material had a weight of 112 g/nf. The properties of this composite molded plate are shown in Table 2.

Comparative Example 1 An isocyanate group-terminated prepolymer (V) was prepared in the following manner.

Millionate MR-1001000 copies and PEG-40
0 (manufactured by Sanyo Chemical Industries, 0HV280) 131 parts and 8
The reaction was carried out at 0°C for 3 hours to obtain an isocyanate group-terminated prepolymer.

The NGO content of this resin was 25.0%. A composite molded plate was manufactured using the hydrophilic polyisocyanate resin (V) thus obtained. The manufacturing conditions were exactly the same as in Example 9, and the amount of resin applied was 132 g/% for the surface material and 106 g/rd for the back surface material. The properties of this composite molded plate are shown in Table 2.

Claims (1)

[Claims] 1. When molding and manufacturing a composite molded plate using the surface material, backing material, core layer material, and back material, water-foamable polyisocyanate resin is used as a binder for the above-mentioned base materials. A method for forming and manufacturing a composite molded plate, characterized by: 2. The water-foamable polyisocyanate resin is an organic polyisocyanate compound containing two or more isocyanate groups in the molecule and/or its isocyanate group-terminated prepolymer, dialkoxylate monoalkylamine, trialkoxylate monoalkyldiamine, The composite molding according to claim 1, which is obtained by reacting one or more types of polyoxyalkylene-added higher aliphatic amine derivatives represented by dialkoxylate monoalkylamide and trialkoxylate monoalkylamide amine. Method of forming and manufacturing plates.