JPH05488A - Method for treating rear face of surface material - Google Patents

Abstract

PURPOSE:To perform rear face treatment of a surface material inexpensively, with good workability and in a short cycle time by using a water-foamable polyisocyanate resin as a rear face treating agent of the surface material when a molded item with a surface material is prepd. CONSTITUTION:This method exhibits especially an excellent effect on a surface material having impregnating properties such as a woven fabric made of glass fiber, cotton, wool, man-made fiber etc. A water-foamable polyisocyanate resin used can be obtd. by reacting an org. polyisocyanate compd. having two or more isocyanate groups in a molecule and/or an isocyanate group-terminated prepolymer thereof with one or two or more polyoxyalkylene-adduct of a higher aliph. amine deriv. A rear face treatment is generally performed by spraying water on the rear face of the surface material and then, coating uniformly it with a water-foamable polyisocyanate resin. The treated surface material is most effective when it is integrally molded with a urethane foam in a closed mold.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating the back surface of a surface material.

More specifically, when manufacturing a molded article with a surface material for automobiles, furniture, housing, etc., an organic polyisocyanate compound and / or its isocyanate group-terminated prepolymer is used as a back surface treating agent for the surface material. 1 of polyoxyalkylene addition higher aliphatic amine derivative
The present invention relates to a method for treating the back surface of a surface material using a water-foamable polyisocyanate resin obtained by a reaction with one or more kinds.

[0003]

2. Description of the Related Art Conventionally, when manufacturing molded articles with surface materials such as automobiles, furnitures, and housings, the surface of polyurethane and resin has been integrated by utilizing the excellent self-adhesive property of polyurethane resin. Molding methods have been adopted.

However, when the polyurethane resin is integrally molded with metals, synthetic resins, leather, etc., even if a compression molding method is adopted, a surface material which is not impregnated with the resin exhibits self-adhesive properties without problems. However, in the case of a surface material such as a colored woven fabric, if the back surface treatment method is not applied, the resin may be impregnated, the feel may be deteriorated, and the resin may penetrate to the surface of the base material.

Therefore, in general, when a base material having an impregnating property is used as a surface material in a compression molding method, for the purpose of preventing resin from impregnating into the surface material or leaching onto the surface of the base material, A method is used in which the back surface of the substrate is directly coated with polyethylene or the like, or in order to further improve the feel, a sheet-like material cut out from a soft slab foam is coated and then polyethylene coated. In this way, it is general to obtain a molded product having the required feel by integrally molding.

However, such a method inevitably raises the cost of the film, and when it is used as a cushioning material in particular, it becomes a serious problem in terms of ventilation and perspiration absorption.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the drawbacks of the conventional surface material back surface processing technology, to reduce the manufacturing cost, to improve the workability of the process, and to shorten the cycle. It is an object of the present invention to provide a back surface processing method for a surface material having time.

As a result of earnest studies and studies, the inventors of the present invention have found that an organic polyisocyanate compound and / or its isocyanate group-terminated prepolymer are treated with a polyoxyalkylene-added higher-grade compound in the back surface treatment of an impregnating surface material. By using a water-foamable polyisocyanate resin obtained by modifying with an aliphatic amine derivative as a back surface treating agent, workability and dispersibility in water are excellent,
In addition, because it has the characteristics that a backside treatment agent that can adjust the foaming resin conversion rate can be obtained and that the foaming resin can be arbitrarily controlled from elastic ones to rigid ones, it has a surface material and water foaming property. It has been found that various combinations with a polyisocyanate resin give backside treated surface materials having various feels, and completed the present invention.

[0009]

That is, the present invention provides a back surface treatment method for a surface material, which comprises using a water-foamable polyisocyanate resin as a back surface treatment agent when treating the back surface of a surface material. is there.

The back surface treatment method of the present invention exhibits excellent effects particularly when applied to a surface material having an impregnating property. The surface material used is typically a colored woven fabric made of glass fiber, cotton, wool, chemical fiber or the like.

Examples of the water-foamable polyisocyanate resin usable in the present invention include organic polyisocyanate compounds having two or more isocyanate groups in the molecule and / or their isocyanate group-terminated prepolymers, and dialkoxylate monoalkylamines. , A trialkoxylate monoalkyldiamine, a dialkoxylate monoalkylamide, and a polyoxyalkylene-added higher aliphatic amine derivative typified by a trialkoxylate monoalkylamide amine.

Examples of the organic polyisocyanate compound for the resin include tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, biphenylene diisocyanate, diphenyl ether diisocyanate, tolidine diisocyanate having two or more functional groups. Hexamethylene diisocyanate, isophorone diisocyanate, etc., such isocyanate derivatives and their similar compounds may be used alone or as a mixture of two or more kinds.

The isocyanate group-terminated prepolymer is obtained by reacting an organic polyisocyanate compound with a polyol having active hydrogen.

Typical polyols having active hydrogen are polyester polyols, polyether polyols, epoxy polyols and the like, and two or more kinds of these polyols can be used in combination.

Examples of the polyester polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, glycerin, One or more compounds having at least two hydroxyl groups such as trimethylolpropane, pentaerythritol and sorbitol, and malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, sebacic acid, oxalic acid and phthalic acid. , Terephthalic acid, azelaic acid, trimellitic acid and the like, and one or more compounds having at least two carboxyl groups can be used to produce them by a known method. Also included are lactone-based polyesters obtained by ring-opening polymerization of monomers having a lactone ring represented by ε-caprolactone and δ-valerolactone.

Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, glycerin, sorbitol, sucrose, bisphenol A, One or two of compounds having at least two active hydrogens such as pentaerythritol
Produced by addition-polymerizing one or more kinds of monomers such as ethylene oxide having 2 or more carbon atoms, propylene oxide and butylene oxide, and monomers such as epichlorohydrin by using one or more kinds as a polyol starting compound by a known method. .

The polyol having these active hydrogens has the general formula:

[0018]

[Chemical 1]

(Wherein R ₃ is an alkyl group and R ₄ is an alkylene group) and has a molecular weight of 250 to 4000.
Alkoxy polyalkylene glycols of are also included.

The polyoxyalkylene-added higher aliphatic amine derivative used in the present invention has the general formula (1),
It is shown by (2), (3) and (4).

[0021]

[Chemical 2]

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

Where:

R: a linear or branched alkyl group or hydroxyalkyl group having an average carbon number of 8 to 40 (provided that an alkenyl group, a hydroxyalkenyl group, a phenyl group, a benzyl group and a group having an ether bond in the carbon chain are also included. )

R _{1 is} hydrogen or a methyl group (however, hydrogen and a methyl group may be introduced randomly or in a block-like combination).

R _{2 is} a linear or branched alkyl group or hydroxyalkyl group having an average carbon number of 7 to 39 (however, alkenyl group, hydroxyalkenyl group, benzyl group and those having an ether bond in the carbon chain are also included).

X ₁ , x ₂ , y ₁ , y ₂ , z ₁ , z ₂ : 1
An integer n of 100: an integer of 2 or 3.

R and R ₂ --CO of the general formulas (1) to (4)
The fatty acid residue of-may be a natural fatty acid residue of plant or animal origin, or may be a synthetic fatty acid residue of chemical synthesis or the like.

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

The animal-derived ones include those obtained from pig oil, beef tallow oil, sardine oil, herring oil, squid oil, sardine oil, whale oil, etc., and the oxygen-containing fatty acid residue is cork oak bark. Some are obtained from oil.

Industrially available methods for synthesizing fatty acids using petroleum as raw materials include liquid-phase air oxidation of paraffin, hydroformylation of olefins (oxo method) or carbonylation (Koch method), and large-scale production is carried out. It is being appreciated.

The fatty acid residues from these animal or vegetable oils or synthetic fatty acids may be used alone or in admixture of two or more.

Examples of such polyoxyalkylene-added higher aliphatic amine derivative include those represented by the general formula (1): dialkoxylate monoalkylamine,
As represented by the general formula (2), a trialkoxy monoalkyl diamine, as represented by the general formula (3), a dialkoxylate monoalkylamide and as represented by the general formula (4), a trialkoxylate monoalkylamide amine. Etc.

When the surface material of the present invention is subjected to the back surface treatment, an inorganic filler, a flame retardant or the like may be added to the water-foamable polyisocyanate resin.

Examples of the inorganic fillers include mica powder, powdered clay, silica gel, gypsum, calcium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, sodium silicate, silica sand, perlite, shirasu balloon and glass balloon. Etc. Such an inorganic filler is also effective as a reinforcing agent and a bulking agent.

As the flame retardant, tris (chloroethyl)
There are halogen organic phosphate compounds such as phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, and halogen-based flame retardants such as decabromodiphenyl oxide. These inorganic or 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 having a relatively low viscosity. For this reason, the resin composition of the present invention does not require a viscosity modifier, but may be added or blended depending on the case. However, organic solvents having a low boiling point, such as acetic acid esters and ketones, are not preferable because of problems of working environment, risk of ignition, and the like. Alkylene carbonates, phthalic acid esters and the like have high boiling points and flash points, and are preferable as a viscosity modifier.

From the water-foamable polyisocyanate resin used in the present invention, foams having various properties can be obtained. That is, changing the type of the organic polyisocyanate compound, changing the structure and molecular weight of the polyoxyalkylene-added higher aliphatic amine derivative which is the compound in the present invention, and producing a prepolymer such as a general-purpose polyester polyol or polyether polyol By changing the type of modifier used for the product, it is possible to freely adjust the foam ratio from a soft foam with elasticity to a hard foam with rigidity, from several times to several tens of times. It has become possible to give the material properties suitable for its use.

The water-foamable polyisocyanate resin of the present invention has extremely high reactivity with water, but it has excellent storage stability in a system in which moisture is blocked, and changes in viscosity and NCO content with time. There is almost no, and it is sufficiently usable after long-term storage.

The back surface treatment of the surface material of the present invention can be generally accomplished by the following method.

Water is previously sprayed on the back surface of the liquid-impregnated base material as the surface material, and then a water-foamable polyisocyanate resin is sprayed, brushed, doctor knife,
Apply evenly using a roller. Further, a method of mixing the resin and water and applying it as an emulsion is also possible. In this case, it is preferable to adopt a method of mixing immediately before coating, and it is possible to coat the base material before the resin is cured by using a collision mixing type spray foaming machine used for spray foaming of polyurethane foam. It will be possible.

The amount applied is determined by the desired foam thickness. After applying the resin, it can be passed through a hot oven for the purpose of accelerating the curing, but the water-foamable polyisocyanate resin of the present invention has extremely large reactivity with water, so that it is cured at room temperature unless there is a special reason. Is enough.

The surface material produced by using the water-foamable polyisocyanate resin of the present invention as a back surface treating agent can be prepared by adjusting the kind of the resin, the kind of the base material, the coating amount of the resin, that is, the foam thickness and the like. Since the hardness, elasticity, feel, etc. of the material can be changed in various ways, it can be applied to an extremely wide range of fields. For example, it can be applied to seat cushions, headrests, armrests, dashboards and the like in automobiles, and wall materials, floors and other furniture materials in housings.

In particular, the back-treated surface material of the present invention is most effective when the urethane foam and the surface material are integrally molded in a closed mold. In other words, since the foam with an extremely thin skin layer is interposed between the urethane foam and the surface material, the impregnation of the injected urethane resin into the surface material can be prevented, and compared to polyethylene coating etc., it is extremely breathable. Since it is rich, it can solve the problem of sweat absorption especially when used as a cushion material.

[0047]

In the treatment of the surface material of the present invention, it is obtained by modifying the organic polyisocyanate compound and / or its isocyanate group-terminated prepolymer as a back surface treating agent with a polyoxyalkylene-added higher aliphatic amine derivative. By adopting water-foamable polyisocyanate resin, it is possible to solve the problems that are likely to occur with the back surface treatment method of the impregnating base material up to now, that is, the cost increase of the film, the adverse effect on ventilation, sweat absorption, etc. Became.

[0048]

EXAMPLES Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.

The polyoxyalkylene addition higher aliphatic amine derivative used in the examples is abbreviated as amine derivative polyol. Unless otherwise stated
Parts and% in the examples and comparative examples represent "parts by weight" and "% by weight", respectively.

Production Example 1 A water-foamable polyisocyanate resin (A) was prepared in the following manner.

Polyphenylmethane polyisocyanate (Nippon Polyurethane Industry, Coronate-1104, N
970 parts of CO content (31.0%) 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 lower, sardine oil amine E15 (alkyl distribution: carbon number 20 to 22 is about 90) as an amine derivative polyol (corresponding to general formula (1)).
%, The number of moles of ethylene oxide added is 15, and the hydroxyl value is 1
43) 235 parts was added while confirming the temperature rise, and finally the mixture was kept at 80 ° C. for 3 hours to obtain a water-foamable polyisocyanate resin (A). The NCO content of this resin is 2
It was 1.8%.

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

Liquid diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry, Millionate MTL, NC
O content 29.0%) 1000 parts and average molecular weight 4700,
A water-foamable polyisocyanate resin was obtained by reacting 336 parts of a random addition polyalkylene diol having an average number of functional groups of 2 and a molar addition polymerization ratio of ethylene oxide and propylene oxide of 80/20 at 80 ° C. for 3 hours. After cooling 1000 parts of this resin to 40 ° C. or lower, a beef tallow diamine E3 (alkyl distribution: carbon number 18 is 2) as an amine derivative polyol (corresponding to general formula (2)) was obtained.
4%, carbon number 18 having one unsaturated bond is 37%, carbon number 16 is 30%, ethylene oxide addition mole number is 3, hydroxyl value 390) 60 parts is reacted in the same manner as in Production Example 1, A water-foamable polyisocyanate resin was obtained. The NCO content of this resin was 19.2%.

Production Example 3 A water-foamable polyisocyanate resin (C) was prepared in the following manner.

Liquid diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry, Millionate MTL, NC
O content 29.0%) 1000 parts and average molecular weight 3000,
An isocyanate group-terminated prepolymer was obtained by reacting 1049 parts of randomly added polyalkylenetriol having an average number of functional groups of 2 and a molar addition polymerization ratio of ethylene oxide and propylene oxide of 90/10 at 80 ° C for 3 hours. After cooling 1000 parts of this resin to 40 ° C. or lower, as an amine derivative polyol (corresponding to the general formula (3)), cured beef tallow amide E50 (alkyl distribution: carbon number 18 is 63%, carbon number 16 is 30). %, The number of moles of ethylene oxide added is 50, and the hydroxyl value is 48) 134 parts were reacted in the same manner as in Production Example 1 to obtain a water-foamable polyisocyanate resin (C). The NCO content of this resin is 10
%Met. This resin 750 because it was a viscous liquid
Part ethylene carbonate and propylene carbonate 1
250 parts of the mixture of Pair 1 was added to reduce the viscosity, and the mixture was used in Example 3.

Production Example 4 A water-foamable polyisocyanate resin (D) was prepared in the following manner.

Self-emulsifying type polyphenylmethane polyisocyanate (Nippon Polyurethane Industry, Coronate 305
3, NCO content 29.3%) As an amine derivative polyol (corresponding to general formula (4)) in 1000 parts, beef tallow amidoamine E15 (alkyl distribution: 24% carbon number 18%, carbon number 18 having one unsaturated bond) Is 37% and has 16 carbon atoms
Of 30%, the number of moles of ethylene oxide added is 15, and 180 parts of a hydroxyl value of 190) were reacted in the same manner as in Production Example 1 to obtain a water-foamable polyisocyanate resin. The NCO content of this resin was 22.0%.

Production Example 5 A water-foamable polyisocyanate resin (E) was prepared in the following manner.

1000 parts of tolylene diisocyanate (Nippon Polyurethane Industry Co., Ltd., Coronate T-80), an average molecular weight of 2900, an average number of functional groups of 2, and a molar addition polymerization ratio of ethylene oxide and propylene oxide of 40/60.
And 553 parts of the randomly added polyalkylene diol were reacted at 80 ° C. for 3 hours to obtain an isocyanate group-terminated prepolymer. After mixing 500 parts of this resin with 500 parts of polyphenylmethane polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MR-200, NCO content 31.2%), 230 parts of the amine derivative polyol used in Example 1 were used. A reaction was carried out in the same manner as in, to obtain a water-foamable polyisocyanate resin. The NCO content of this resin was 20.9%.

Production Example 6 An isocyanate group-terminated prepolymer (F) to be used in Comparative Examples was prepared in the following manner.

Polyphenylmethane polyisocyanate (Millionate MR-10 manufactured by Nippon Polyurethane Industry Co., Ltd.)
0, NCO content 30.9%) 1000 parts and PEG-40
0 (manufactured by Sanyo Chemical Industries, hydroxyl value 280) 131 parts 8
The reaction was carried out at 0 ° C for 3 hours to obtain an isocyanate group-terminated prepolymer. The NCO content of this resin was 25.0%.

Using the resins prepared in Production Examples 1 to 6, the surface material was subjected to back surface treatment and used as a base material for molded articles.

Example 1 As the surface material, a backside untreated colored woven fabric was used. Water-foamable polyisocyanate resin (A) prepared in Production Example 1
Was used for the back surface treatment. Water on the back of the surface material 5
After applying 0 g / m ² spray, the resin was uniformly applied using a roller. The amount of resin applied was 210 g / m ² . The foaming started at the same time as the coating was completed, and the foaming ended after 1 minute. The average thickness of the foam layer is 2.3 mm,
It had a very thin skin layer.

Using this back-treated colored woven fabric as the surface material, a molded foam was prepared. The formulation used for foaming is as shown in Table 1, which is a general one used for a front seat cushion, and the free rise foam density was 42 kg / m ³ and the rise time was 87 seconds. The integrally molded foam body obtained with the obtained surface material had an extremely excellent feel and had physical properties sufficient for use as a front seat cushion.

[0065]

[Table 1]

Example 2 Using the water-foamable polyisocyanate resin (B) prepared in Production Example 2 under the same conditions as in Example 1, a colored woven fabric subjected to a back surface treatment was used as a surface material, and foamed by molding. Created the body. The results were the same as in Example 1, and both the feel and the physical properties were sufficient for use in the front seat cushion.

Example 3 Using the water-foamable polyisocyanate resin (C) prepared in Production Example 3 and subjecting the colored woven fabric subjected to the back treatment under the same conditions as in Example 1 as the surface material, molding foaming Created the body. The result was that the integrally molded mold foam obtained in Example 1 had a slightly harder feel, but was excellent in impact resilience and had physical properties sufficient for use as a front seat cushion.

Example 4 As the surface material, a backside untreated colored woven fabric was used. Water-foaming polyisocyanate resin (D) prepared in Production Example 4
Was used to perform the back surface treatment. 200 g of water and 300 g of water-foamed polyisocyanate resin were mixed in advance to form an emulsion, which was then applied by air spray to the back surface of the base material so that the resin application amount was 250 g / m ² . The foaming started at the same time as the coating was completed, and the foaming ended after 1 minute.
The foam layer had an average thickness of 2.5 mm and had an extremely thin skin layer.

A molded foam body was prepared by using the colored woven cloth subjected to the back surface treatment as a surface material. The formulation used for foaming is as shown in Table 2, which is a general one used for headrests and has a free rise foam density of 50 kg.
/ M ³ , and the rise time was 97 seconds. The integrally molded mold foam with the obtained surface material had a very soft feel and had physical properties sufficient for use in a headrest.

[0070]

[Table 2]

Example 5 Molded foam using as a surface material a colored woven fabric which was treated on the back side under the same conditions as in Example 1 using the water-foamed polyisocyanate resin (E) prepared in Production Example 5. It was created. The integrally molded product thus obtained was slightly soft to the touch and was sufficient for use as a front seat cushion excellent in impact resilience, elongation properties and tear properties.

Comparative Example 1 Using the isocyanate group-terminated prepolymer (F) prepared in Production Example 6, the back surface of a colored woven fabric having no back surface was treated under the same conditions as in Example 1, but a foam was obtained. It was slow to rise, and the colored woven fabric was impregnated with the resin, so that it was not possible to obtain a material having a feel that could be used as a surface material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08J 7/04 7258-4F C09J 175/04 JFA 8620-4J D06M 15/564

Claims (2)

[Claims] 1. A method for treating the backside of a surface material, wherein a water-foamable polyisocyanate resin is used as a backside treating agent when treating the backside of the surface material. 2. A water-foamable polyisocyanate resin comprising an organic polyisocyanate compound and / or an isocyanate group-terminated prepolymer thereof and a dialkoxylate monoalkylamine, trialkoxylate monoalkyldiamine, dialkoxylate monoalkylamide and trialkoxy. The method for treating the back surface of the surface material according to claim 1, which is obtained by reacting with one or more polyoxyalkylene-added higher aliphatic amine derivatives selected from the group consisting of rate monoalkylamidoamines.