WO1990006973A1

WO1990006973A1 - Polyurethane molding

Info

Publication number: WO1990006973A1
Application number: PCT/JP1989/001255
Authority: WO
Inventors: Shintaro Tachibana
Original assignee: Md Kasei Limited
Priority date: 1988-12-15
Filing date: 1989-12-14
Publication date: 1990-06-28
Also published as: JPH02163160A; AU4742790A; KR910700314A

Abstract

This invention relates to a polyurethane molding and a method for producing the same. This molding is characterized by containing a discoloration inhibitor added to a polyurethane molding produced by forming a coating film containing aluminum powder on the surface of a molding of polyurethane prepared in the presence of a catalyst comprising a tertiary amino. The discoloration inhibitor is selected from among the compounds of formulae (1) and (2), wherein 1«n«3 and R represents an alkyl or phenyl group which may be substituted.

Description

Description Polyurethane molded product technology field

The present invention relates to a polyurethane molded article having a coating film (metallic coating film) having aluminum powder formed on its surface, and particularly to a metallic coating film. The present invention relates to a polyurethane molded article having improved discoloration resistance. Background technology

Polyurethane molded products with a coating film formed on the surface are used for automotive parts, electronic and electrical equipment parts, etc. according to their physical properties. In recent years, automotive bumpers and air spoilers have been used. Applications to automotive exterior parts such as folders and door panels, and electronic and electrical equipment parts such as computers and air conditioner housings are increasing.

Polyurethane molded articles are usually introduced in the presence of a tertiary amine catalyst into a mold capable of sealing a reaction mixture consisting of polyisocyanate, polyol, a crosslinking agent and additives. Manufactured.

Polyurethane molded products as parts for automobiles and electronic and electrical equipment are usually painted on their surfaces for the purpose of design and improvement of weather resistance.

However, a conventional polish with a coating film containing aluminum powder on the surface When urethane molded products are exposed to high humidity atmosphere or come into contact with water, tertiary amine (catalyst of urethanization reaction) in polyurethane molded products and water There was a drawback that the aluminum powder in the coating film was corroded by the action of, and the coating film was discolored.

"Disclosure of the invention

The inventors of the present invention have conducted various studies on the improvement of the discoloration resistance of a polyester molded product having a metal coating film formed on the surface thereof, and have reached the present invention.

That is, the present invention provides a foamed or non-foamed polyurethane by reacting in a mold in the presence of a polyisocyanate, a polyol, a tertiary amine catalyst, and if necessary, a foaming agent and other additives. The following general formula is used as a discoloration inhibitor when a resin is molded to form a coating having aluminum powder on the surface of the molded product.

A polyurethane molded article characterized by containing the compound represented by (1) or (2).

(CH ₃ 0) _n PR ₃ - _n (1)

0

II

CH ₃ 0-SB -——--(2)

II

0

(In the general formula, 1 ^ η≤3, and R represents an alkyl group or a phenyl group which may have a substituent.) BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the compound represented by the general formula (1) include, for example, trimethylethyl phosphate, dimethylethyl methylphosphonate, dimethylethylphenylphosphonate, dimethylethyltrilyphosphonate, and dimethylphosphonate. Examples thereof include methyl phosphinate and methyl diphenylphosphinate.

Examples of the compound represented by the general formula (2) include methyl benzenesulfonate, methyl p-toluenesolefonate, methyl ethanesulfonate and the like.

These discoloration inhibitors may be used alone or as a mixture thereof. In the present invention, the amount of the discoloration inhibitor used is usually 0.2 to 2% by weight, preferably 0.3 to 1.5% by weight, based on the following polyurethane molded article.

As the polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. Such polyso- cinates include aromatic polyso- cnates (eg, 2,4 and / or 2,6—trendrange soci- nate (TDI), crude TDI, 2,4_ And / or 4,4'-diphenylmethanediisocyanate (MDI), crude MDI, etc., aliphatic polyisocyanate (e.g., hexadiethylenediisomethane, isohodium) Modified products (urethane group, carbodimid group, etc.) of these compounds (e.g., xylylene diisocyanate, etc.) and araliphatic aliphatic isocyanates (eg, xylylene diisocyanate) , Urethane imine group, isocyanurate group, oxazolidone And mixtures of these two or more.

Polyols used in the present invention may be those conventionally used in the production of polyurethane. Such polyols include, for example, polyether diols, polyester polyols and polyethylene polyols. These polyols usually have 2 to 8 hydroxyl groups in one molecule, and their 0H values are about 20 to SOO m KOH Z g.

In the present invention, a crosslinking agent may be used. Examples of the crosslinking agent used include low molecular weight diols (eg, ethylene glycol, diethylene glycol, propylene glycol, dipropylen glycol, 1,4-butanediol, 1,6-hexanediol, etc.), and alkanols Minamine (for example, monoethanolamine, diethanolamine, triethanolamine, monopropanol amine, tripronodinolamine, etc.), aliphatic polyamine (for example, ethylenediamine) Min, trimethylenediamine, tetramethylenediamine, diethylenetriamine, etc.), aromatic polyamine (for example, fudylenediamine, tridiamine, getyl) Tolylenediamine, difuunilmethandiamine, methylenebis (0—chlorine And mixtures of two or more of these.

The amount of cross-linking agent used is usually 5 to 40% by weight, preferably 10 to 30% by weight, based on the weight of voryl.

A tertiary amine is used as a catalyst for the polyurethanation reaction used in the present invention. good.

As tertiary amine catalysts, for example, triethylamine, triethylenediamine, 2-methylthioethylenediamine, N, N, N ', N'ate Lamethylethylamine, N, N, N ', N'—Tetramethylhexenemethylamine, NN, N', N'Tetramethylpropylamine, N, NN ', N', N "-pentamethylinoethylentriamine, trimethylethylaminoethylinoperipazine, N, N '-dimethylsilicone, N, N' — Dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, and mixtures thereof can be used.

The amount of tertiary amine catalyst used is usually 0.1 to 5% by weight based on the total weight of the polyol and crosslinking agent.

As the tin-based catalyst, dibutyltin dilaurate, stannous octoate, and the like can be used, and the amount of the catalyst is usually 0.005 to 1 weight based on the total weight of the polyol and the cross-linking agent. %.

In the present invention, a foaming agent (for example, trichloro monofluoromethane, dichloromethane, water, etc.) can be used as necessary in the production of polyurethane.

The amount of foaming agent used is 1 to 10% by weight in the case of tricyclo-te-no-fuzoreo-meta or dichloromethane, based on the sum of the weights of bolol and crosslinker II. In the case of water, it is 0.1 to 2% by weight. In the present invention, when molding polyurethane, the NC 0 index [equivalent ratio of the active hydrogen atom-containing group X100] is 100. Usually 80-120, preferably 95-108.

The coating material for forming a coating film containing aluminum powder used in the present invention is usually composed of a hardening resin having 1 to 5% by weight of aluminum powder, and the hardening resin is a two-pack type polyester resin. , Two-component acrylurethane, melamin-cured urethanepolyester, and the like can be used. Specifically, paints for elastomers 8257 / ^ 230 (Nippon Bi-Chemical Co., Ltd.), Soflex 1400 (Kansai Paint Co., Ltd.), Branit 11160 (Dainippon Co., Ltd.), A paint such as M130 (Dainippon Paint Co., Ltd.) can be used.

Such a paint is applied to the surface of the polyurethane molded article by spraying or the like, and then baked and cured to form a coating film.

The polyurethane molded article containing the specific compound of the present invention has excellent resistance to discoloration of the metallic coating film even if a coating film containing aluminum powder is formed.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the examples, "part J" indicates "parts by weight".

The raw materials used in Examples and Comparative Examples are as follows.

(1) Discoloration inhibitor

TMP: Trimethyl phosphate

DMMP: dimethyl methyl phosphate

D PP: Dimethyl phenylphosphonate

MBS: methyl benzenesulfonate (2) Catalyst

DBTDL: Dibutyltin dilaurate

DABC033LV: Triethylenediamine 33% dipropylene glycol solution

(3) Polyol A: A trifunctional polyol having a 0H value of 28 ingKOHZ g, in which 92 parts of glycerin are added with 4700 parts of propylene oxide and then 1200 parts of ethylenoxide. '

(4) Emulsifying agent: ethylene glycol

(5) Isolation

Isonata 143L: Carbodi

Denatured M D I (1 ^ (: 0 occupancy rate 28.3%)

(6) Paint

Paint A: Two-component polyester urethane paint

Aluminum powder content 4%

Paint B: One-component mela-mine cured acrylic paint

Aluminum powder content 4%

Examples 1 to 9, Comparative Examples 1 and 2

According to the formulation shown in Table 1, under the following molding conditions, a polyol premix composed of a polyol, a crosslinking agent and a catalyst and an isocyanate were charged into a raw material tank of a high-pressure foaming machine, respectively. The reaction mixture obtained by collision mixing at the sing head is poured into a temperature-adjustable closed mold with a thickness of 3.0 讓 X width 550 卿 X length 600 を to form a polyurethane molded product. did. The anti-tarnish agent was added to the polyol premix in Examples 1 and 2, and to the isocyanate in Examples 3 to 9. Thus, a molded product was obtained.

〔Molding condition〕

High pressure foaming machine HD500 (Admiral high pressure foaming machine) Discharge speed 500 g Z sec

Discharge pressure 150 ~ 170kg no αί

Raw material temperature 40 S 2 X

Mold temperature 70 ± 2

A sample of 70 mm wide and 150 cm long was prepared from the obtained polyurethane molded article, washed for 1 minute in ethane vapor of a tricyclo mouth, dried for 10 minutes at room temperature, and then subjected to Examples 1 to 9 Further, the samples of Comparative Examples 1 and 2 were arranged at the same time, and the paint A or paint B was used as a fan. After spraying with a spray gun, the coating was heated and baked after setting for about 10 minutes to obtain a coating sample. When paint A was used, baking was performed at 100'C for 30 minutes, and when paint B was used, baking was performed at 120'C for 30 minutes.

The discoloration resistance of the obtained coated sample was determined by immersing the coated sample in ion-exchanged water adjusted to 40 to 240 hours, and then measuring the degree of discoloration of the coating film before and after immersion using a colorimeter. The evaluation was made by measuring the Hunter color difference E (Lab) using the tester and performing visual judgment. The evaluation results of the color fastness are shown in Section 1 袠. Table 1 (Part 1) Example of implementation

Prescription (part)

1 2 3 4 5

Isonate 1 88.4 88.4 88.4 88.4 88.4

(NC0

(Defux) (104) (104) (104) (104) (104) Polyol A 84 84 84 84 84 Ethylene

Glycol 16 16 16 16 16

DABCO 33LV 1.5 1.5 1.5 1.5 1.5

DBTDL 0.05 0.05 0.05 0.05 0.05

TMP U.4 丄, U.44 1 丄, oo ^

Strange

DMMP U.44 color

DMPP---

Prevention

MBS ― ― ― ― Temporary

Anti-discoloring agent Poly-ol-so-sia-so-sia-isol-added all-all-nate-nate component

Paint A

J ΔE (Lab) 0.7 0.3 0.3 0.2 0.5

¹ Visual judgment No discoloration No discoloration No discoloration No discoloration No discoloration Color paint B

J Δ E (Lab) 0.8 0.5 0.9 0.4 0.7

^One hundred vision judgment No discoloration No discoloration No discoloration No discoloration No discoloration Table 1 (Part 2)

Industrial applicability

The present invention provides a molded article of polyurethane which can be advantageously used for parts for automobiles, parts for electronic and electric equipment, and the like.

Claims

An example of billing! ! "

1. Polyurethane molded products in which a coating film containing aluminum powder is formed on the surface of a polyurethane molded product produced using tertiary amine as a catalyst. A polyurethane molded article characterized by containing a compound represented by the following general formula (1) or (2).

(CH ₃ 0) _n PR ₃ -n .C 1)

II

0

II

CH ₃ 0-SR (2)

-II

0

(In the general formula, l ≤ n ≤ 3, and R is an alkyl group or a fuunyl group which may have a substituent.)

2. The compound represented by the general formula (1) is a compound represented by the following formula: trimethyl phosphate, dimethyl methyl phosphonate, dimethyl phenyl phosphonate, dimethyl methyl triphosphonate, methyl dimethyl phosphinate and dimethyl The molded article according to claim 1, wherein the molded article is selected from methyl nylphosphinate.

3. The composition according to claim 1, wherein the compound represented by the general formula (2) is selected from methyl benzenesulfonate, methyl P-toluenesulfonate and methyl ethanesulfonate.

4. The compound according to claim 1, wherein the compound represented by the general formula (1) or (2) is compounded in an amount of 0.2 to 2% by weight with respect to the polystyrene molded article. Composition.

5. The composition according to claim 4, wherein the amount is 0.3 to 1.5% by weight.

6. The polyisocyanate and polyol are reacted in a mold in the presence of a tertiary amine catalyst and, if necessary, a foaming agent and other additives to form a foamed or non-foamed polyurethane. The following general formula (1) or (1) is used as a discoloration inhibitor in the production of a polyurethane molded product by forming a resin and forming a coating film containing aluminum powder on the surface of the molded product. 2) A method for producing a polyurethane molded product, which comprises compounding the compound represented by the formula (2).

(CH ₃ 0) _n PR ₃ -»(1)

II

0

II

CHsO-S-R (2)

II

0

(In the general formula, 1 ^ η≤3, and R represents an alkyl group or a phenyl group which may have a substituent.)

7. The compound represented by the general formula (1) is a compound represented by the following formula: trimethyl phosphate-dimethyl dimethyl phosphonate, dimethyl phosphonate dimethyl, methyl trifluorophosphonate, methyl dimethyl phosphinate 7. The method according to claim 6, wherein the method is selected from methyl and methyl diphenylphosphinate.

8. The method according to claim 6, wherein the compound represented by the general formula (2) is selected from methyl benzenesulfonate, methyl P-toluenesulfonate and methyl ethanesulfonate. .

9. The method according to claim 6, wherein the compound represented by the general formula (1) or (2) is blended in an amount of 0.2 to 2% by weight with respect to the polyurethane molded article. .

10. The method according to claim 9, wherein the amount is 0.3 to 1.5% by weight.

11. The polyisocyanate is selected from aromatic polyisocyanates, aliphatic polyisocynates, araliphatic isocyanates, modifications thereof, and mixtures of two or more of these. 7. The method of claim 6, wherein:

12. The method according to claim 6, wherein the polyol is selected from polyether polyols, polyester polyols and polymer polyols.

13. The method according to claim 6, wherein a cross-linking agent selected from low molecular diols, alkanolamines, aliphatic polyamines, aromatic polyamines, and mixtures of two or more thereof is used. Law.

14. The method according to claim 13, wherein the amount of the cross-linking agent used is 5 to 40% by weight based on the weight of voryl.

15. When the tertiary amine catalyst is triethylamine, triethylenediamine, 2-methyltriethylenediamine, N, N,

N ', Ν' — Tetramethylethylamine, Ν, Ν, Ν 'Ν' Tetramethylhexenedimethylamine, ,, Ν, Ν 'Ν' Tetramethylethylpropylene Pentamine, Ν, Ν, Ν ', Ν', Ν "—pentamethylethylethylentriamine, trimethylaminominoethylbiperazine, Ν, Ν '—dimethylcyclohexane 7. The method according to claim 6, wherein the method is selected from silamin, N, N'-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine and a mixture thereof.

16. The method according to claim 15, wherein the tertiary amine catalyst is used in an amount of 0.1 to 5% by weight, based on the total weight of the polyol and the crosslinking agent. '

17. Select from dibutyltin dilaurate and stannous octoate with tertiary amine catalyst.

7. The method according to claim 6, wherein a tin-based catalyst is used.

18. The method according to claim 17, wherein the amount of the tin-based catalyst used is 0.005 to 1% by weight based on the total weight of the polyol and the crosslinking agent.

19. The method according to claim 6, wherein the blowing agent is selected from trichloro mouth monofluoromethane, dichloromethane and water.

20. The method according to claim 6, wherein a paint made of a curing resin containing 1 to 5% by weight of aluminum powder is used to form a coating film having aluminum powder.

21. The method according to claim 20, wherein the curing resin is selected from two-part polyester urethane, two-part acrylic polyester, and melamine-cured polyester polyester.