JPS6071625A - Production of polyurethane resin containing inorganic filler - Google Patents

Abstract

PURPOSE:In the production of a polyurethane resin filled with an inorganic fillerfrom a polyol component, isocyanate component and inorganic filler, a specific organic titanate is added in a specific amount to give the titled polyurethane resin with low viscosity and improved thermal stability. CONSTITUTION:The objective polyurethane resin is obtained by adding 0.1- 2pts.wt., per 100pts.wt. of the inorganic filler, of an organic titanate of the formula (R is monovalent 3-8C hydrocarbon group; R' is monovalent 1-18C hydrocarbon group; R'' is divalent 1-8C hydrocarbon group; X, Y, Z are 1, 2; X+Y+Z is 4) to (A) the polyol component such as polyether polyol, (B) the isocyanate component and (C) an inorganic filler such as metal. USE:Sealant, coating.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an inorganic-filled polyurethane resin, and in particular, an inorganic-filled polyurethane resin that has low viscosity even when containing a large amount of inorganic filler, and has improved thermal stability of the cured resin. The present invention relates to a method for producing polyurethane resin.

Inorganic-filled polyurethane resins are used in sealants, paints, adhesives, etc. Inorganic-filled polyurethane resins are usually obtained by adding and mixing an inorganic filler to a more stable polyol component, then mixing the isocyanate component and reacting, because the NCO group in the inocyanate component is highly reactive. .

However, when mixing a polyol component with an inorganic filler in a large amount, the viscosity of the mixed system becomes extremely high due to the high amount of inorganic filler, which causes extremely difficult drawing performance.Also, Generally, polyurethane resins have a drawback in thermal stability, and therefore, mineral-filled polyurethane resins are no exception, and in particular, the decrease in hardness due to heat is significantly large.

The present invention has been made in view of the above-mentioned problems, and is an inorganic material that exhibits little increase in viscosity even when filled with an inorganic filler at a high level, and further improves the thermal stability of the resin obtained by curing. The purpose is to provide a method for producing filled polyurethane resin.

It has been discovered that the above object can be achieved by adding a certain organic titanate compound, and the present invention has been completed.

That is, the present invention provides a method for producing an inorganic-filled polyurethane resin from a polyol component, an isocyanate component, and an inorganic filler, by adding 0.1 to 5 parts by weight of the following general formula [1] to 100 parts by weight of the inorganic filler. ] This is a method for producing an inorganic-filled polyurethane resin, which is characterized by the addition of an organic titanate compound shown in the following.

Ti(OR)x(OCOR')Y(OCOR''NH2
)z ・・＋・＋＋＋++ CI) (In the formula, R is a monovalent hydrocarbon group having 3 to 8 carbon atoms, R' is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R" is a monovalent hydrocarbon group having 1 to 18 carbon atoms. or 8-2
is a valent hydrocarbon group, xyz is 1 to 2, X+Y+
Z=4. ) The polyol component in the present invention refers to various polyols used as raw materials for polyurethane resins, such as polyether polyols, polyester polyols, and polyacrylic polyols, and the molecular weight of these polyols is not particularly limited.

As the incyanate component, a wide range of materials conventionally known as raw materials for polyurethane resins can be used, such as aromatic, aliphatic, and alicyclic isocyanates, and even prepolymerized incyanates. , Specific examples include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, naphthalene diisocyanate, quinrille/diincyanate, bis(isocyanatemethyl)cyclohexane, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, etc. Also used are urethane prepolymers which can be KOed by reacting a lower polyfunctional compound having a plurality of functional groups having active hydration with the above-mentioned diisocyanate.

Various inorganic fillers are used depending on the purpose for which it is used, such as metals, metal oxides, calcium carbonate, talc, clay, carbon black, and wolast, which are used in high fillers as fillers. Knight et al.

The organic titanate compound of general formula [1] in the present invention is Ti (OR) x (OCOR' ) y (OCOR
''NH2)z, where R is a monovalent hydrocarbon group having 3 to 8 carbon atoms, R'' is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R'- is a carbon number 1 to 8 divalent hydrocarbon group, xyz is 1 to 2, x+y+Z=
It is 4.

The monovalent hydrocarbon group having 3 to 8 carbon atoms for R herein may be an alkyl group, alkenyl group, aryl group, etc., and the monovalent hydrocarbon group having 1 to 18 carbon atoms for R' may include an alkyl group, an alkenyl group, an aryl group, etc. , an alkyl group, an alkenyl group, an aryl group, and a divalent hydrocarbon group having 1 to 8 carbon atoms for R'' includes an alkylene group, an iri-lene group, etc. As a specific example, T i (OC3H7) (OCOCH=CH2
)2 (OCO(CH2)5NH2)Ti (QC3H
7) (OCOC□7H3s )2 (OCO(CH2
)5 NI2 :)Ti(OC3H7)(OCO@)2
[0CO(CII2)5NH2]Ti (QC3H7)
(OCOC□7H35) C0CO(CH2)5NH
2'12T 1 (OC3H7) (OCOCR"CH
2) (OCOC17H35) (OCO(CH2) 5
NI2) Ti(OC4H9) (OCOC17H35)2 (O
CO(CH2)5NH2)T i (OC4H9) 2
(OCOC□7H35) (OCO(CH2)5NH
2) T i (OCsH17)2 (OCOC17Ha
s ) (OCO(CH2) 5 NI(2)T i
(OCH2CH”CH2) (OCOC,H2S)2
(OCO(CH2) 5 NI2 ]Ti (QC6
H5) (OCOC□7H3,)2 (0CO(CH2
)5NH21) and the like.

These organotitanate compounds are 1'l (OR)4
It can be easily obtained by reacting R'C0OH with H2NR''C00II.

These organic titanate compounds are effective alone or as a mixture of two or more, and may be added to the polyol component in advance, or may be added simultaneously when mixing the inorganic filler with the polyol component, or may be added to the polyol component at the same time as the inorganic filler. The surface of the compound may be coated in advance, and the method of adding the compound is not particularly limited.

Tora's organic titanate compound is added in an amount equal to 1 inorganic filler.
The amount is from 0.1 to 5 parts by weight, preferably from 0.5 to 2 parts by weight. If the amount is less than 0.01 parts by weight, the effect is small, and even if it is added in amounts of 5 parts by weight or more, no increase in the effect is observed.

In the present invention, various other additives such as a catalyst, a crosslinking agent, a chain extender, and a coloring agent may be used as required.

According to the method of the present invention, by adding a small amount of an organic titanate compound represented by the general formula CI) during the production of an inorganic-filled polyurethane resin, the workability is significantly improved, and the inorganic material is further improved in thermal stability. A filled polyurethane resin can be obtained. Therefore, the present invention is extremely effective for producing inorganic-filled polyurethane resins used in sealants, paints, adhesives, vehicle parts, and the like.

EXAMPLES The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited only to these Examples. Note that parts and parts in the examples indicate parts by weight and weight %.

Examples 1 to 5, Comparative Example 1 Polyether polyol NK-3050K (Mitsui Nisso Urethane G→, trade name) was first mixed with ethylene glycol and dibutyltin dilaurate in the formulation shown in Table 1, and then a historic titanate compound (1 ) Deroru Ti (QC3H
7) (OCOC1□H35)2(OCOC6H4NH
2) (hereinafter referred to as compound (I)). ) was added and mixed, and calcium carbonate (manufactured by Shiroishi Koshou GM) was further added and mixed with (2) as a filler.

The viscosity of the mixture thus obtained was measured and the results are shown in Table 1. The viscosity was also measured for the mixed system without addition of compound [1-1], and the results are shown in Table 1 as a comparative example.

Example 6, Comparative Example 2 First, 30 parts of dioctyl phthalate was mixed with 100 parts of polyether polyol Dial-3000 (manufactured by Mitsui Nisso Tsuretan, trade name), and then Ti (OC3H7), which is an organic titanate compound (1), was mixed with 30 parts of dioctyl phthalate. ) (OCO17H3
5) 0.6 part of 2 (OCO(CH2)5NH2) (hereinafter referred to as compound (1-2,1)) was added and mixed, and further 60 parts of calcium carbonate (ex. 111) was added and mixed.

The viscosity of the mixture thus obtained was measured and the results are shown in Table 2. The viscosity of the mixed system without addition of compound [1-2] was also measured, and the results are shown in Table 2 as Comparative Example 2.

Example 7 In Example 6, Ti (QC3H7) (OCOC,7Ha) was used instead of 066 parts of the compound [:l-2).
Example 6 except that 06 parts of (OCO(CH2)5NII2)2 (hereinafter referred to as compound (1-3)) was used.
I did exactly the same thing. The results are shown in Table-2.

Example 8 In Example 6, Ti (OC3H7) (0COC(C)la) = instead of 0.6 part of compound (1-2)
CH2)2 C0CO(CH2)sNH2) (hereinafter,
It is called compound (1-4). ) was carried out in exactly the same manner as in Example 6 except that 06 parts of the sample were used.

The results are shown in Table-2.

Comparative Example 3 In Example 6, Ti (OC3fI7), a commercially available organic titanate compound, was used instead of 0.6 part of compound (1-2).
The same procedure as in Example 6 was carried out except that 306 parts of (ococmTH&l) was used. The results are shown in Table-2.

Comparative Example 4 In Example 6, T i (OCaHy), a commercially available organic titanate compound, was used instead of 0.6 part of compound (1-2).
Table 2 shows the results obtained in exactly the same manner as in Example 6 except that 0.6 part of COCO(CH2)5NH2)3 was used. The organic chicknate compound used here was in powder form and was extremely difficult to mix and disperse.

Table 2 Examples 9 to 11, Comparative Example 5 MDI-LK (manufactured by Mitsui Nisso Urethane 1η, trade name) was added as an isocyanate component to each of the mixtures obtained in Examples 2 to 4 with NCO10H = 1.05. After mixing at room temperature, pour into a mold and heat at 120℃.
It was cured for 2 hours. Furthermore, heat treatment was performed at 100℃ for 4 days, and the hardness before and after heat treatment was It! II was determined. The results are shown in Table-3.

The mixture obtained in Comparative Example 1 was also tested in the same manner, and the results are shown in Table 3 as Comparative Example 5.

Example 12, Comparative Example 6 First, 25 parts of ethylene glycol, 0.2 parts of dibutyltin dilaurate, and 60 parts of dioctyl phthalate were mixed into 200 parts of polyether polyol EP-330C (manufactured by Mitsui Nisso Tsuretan ■, trade name). Next, 1.2 parts of the above compound (1-2) as an organic titanate compound were added and mixed, and further 120 parts of calcium carbonate (described above) were mixed therein. Next, M as an incyanate component was added to this mixture.
DI -LK (previously) 31.6 parts CNCO10I (=
1.05) was added and mixed at room temperature, then poured into a mold and cured at 120°C for 2 hours. 100 more
Heat treatment was performed at ℃ for 4 days, and the hardness before and after the heat treatment was measured. The results are shown in Table 4.

In addition, a similar test was conducted on a system in which the above compound (1-2) was not added, and Comparative Example 6<! :The results are shown in Table-4.
Shown below.

Example 13 The same procedure as in Example 12 was conducted except that 1.2 parts of the compound (1-4) was used instead of 1.2 parts of the compound (1-2). The results are shown in Table 4.

Table-4 Procedural amendment filed in January 1982 Patent Application No. 178171 2, Title of invention Method for producing inorganic-filled polyurethane resin 3, Relationship with the person making the amendment Patent applicant [companion] ] 100 2-2-1 Otemachi, Chiyoda-ku, Tokyo (4
30) Representative of Nippon Soda Co., Ltd. - Takeo Sannomiya 4, Agent ■ 100 2-2-1 Otemachi, Chiyoda-ku, Tokyo Nippon Soda Co., Ltd. Phone: (245) 6234 6. Contents of the amendment (1) Details Correct rR''J on page 5, line 8 of the book to rR'J.

(2) Correct rNK-3050KJ in the third line of page 8 to rMN-3050KJ.

Claims (1)

[Claims] (1) When producing an inorganic-filled polyurethane resin from a polyol component, an incyanate component, and an inorganic filler, an organic titanate represented by the following general formula [1] in an amount of 01 to 5 parts by weight per 100 parts by weight of the inorganic filler is used. A method for producing an inorganic-filled polyurethane resin, which comprises adding a compound. Ti (OR)x (OCOR′)y (OCOR″N
H2)z -C1''J (wherein, R is a monovalent hydrocarbon group having 3 to 8 carbon atoms, R' is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R// is a monovalent hydrocarbon group having 1 to 18 carbon atoms. 8 divalent hydrocarbon group, xyz is 1 to 2, and X+Y+Z=4.)