JPH01197513A - Preparation of polyurethane resin - Google Patents

Abstract

PURPOSE:To provide excellent adhesiveness, by reacting an alkyl ketene dimer in an appropriate stage of the reaction in preparing a polyurethane resin by reacting an org. polyisocyanate, a high-molecular polyol and a chain extender. CONSTITUTION:In preparing a polyurethane resin by reacting an org. polyisocyanate compd. (A) (e.g., tolylene diisocyanate), a high-molecular polyol compd. (B) (e.g., polycaprolactonediol) and a chain extender (C) (e.g., isophoronediamine), an alkyl ketene dimer (e.g., stearyl ketene dimer) is reacted therewith in an appropriate stage of the reaction. As the obtd. polyurethane resin has excellent adhesiveness to various plastic molded items, it is suitably used as a vehicle for paints, printing inks, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for producing a polyurethane resin, and particularly provides a method for producing a polyurethane resin useful as a coating composition.

[Prior Art] Conventionally, coating compositions for plastic molded products include:
For example, polyurethane resins have been widely used as vehicle components in printing inks and paints. Polyurethane resins are mainly polyisocyanate compounds,
It is produced by the reaction of a polymeric polyol compound, a chain extender, etc.

Although coating compositions containing polyurethane resin as a vehicle component exhibit good adhesion to substrates such as polyester, nylon, or cellophane, they do not adhere well to polyolefin substrates such as polypropylene film. Since this does not provide sufficient adhesion, there is a strong desire for improvement.

Recently, there have been proposals to improve polyurethane resins by introducing groups having a specific chemical structure into them. (JP-A-59-172564, JP-A-61-
No. 91269, JP-A-61-95018, JP-A-61
-141721, JP-A-62-70458) [
Problems to be Solved by the Invention] However, the actual situation is that the adhesion to the b1 boriz 1-11 pyrene film is not necessarily sufficient in the coating composition having the above-proposed polyurethane resin as a vehicle component.

The present invention is applicable to various plastic molded products, especially poly[J]
The object of the present invention is to obtain a polyurethane resin useful as a vehicle component of a coating composition that exhibits good adhesion to pyrene film.

[Means for Solving the Problems] The present inventors have discovered that the above object can be achieved by avoiding the reaction of alkyl ketene dimers at the desired stage in the production process of conventionally known polyurethane resins. This discovery led to the completion of the present invention. That is, the present invention provides a method for producing a polyurethane resin by reacting (a) an organic polyisocyanate compound, (b) a polymeric polyol compound, and (c) a chain extender, and at any stage of the above reaction. (d) A method for producing a polyurethane resin characterized by reacting an alkyl ketene dimer.

As the component (a) used in the present invention, generally known organic polyisocyanate compounds can be used, such as toluene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, diphenylmethane. Aromatic diisocyanates such as diisocyanate, hexamethylene diisocyanate,
Aliphatic or alicyclic diisocyanates such as isoborone diisocyanate and dicyclohexylmethane diisocyanate-1, triisocyanate obtained by trimerization reaction of the above diisocyanate, or a preliminary reaction product of L diisocyanate and a polyol compound. Polyisocyanate prepolymers and the like can be used.

The above polyisocyanate compounds can also be used in combination of two or more.

The component (b) of the present invention, that is, the high-molecular polyol compound, has a terminal hydroxyl group of 211L] or more, and has a molecular weight of about 500 to 5000, particularly 1000 to 3
000 is suitable, and any polymeric polyol compound known in the art can be used. For example, glycols, triols, or higher polyols having polyether chains selected from polyoxyethylene, polyoxypropylene, polyoxytetramethylene, etc., polycarbonate polyols, polylactone polyols, and polybasic acids and polyvalent polyols. Polyester polyols obtained through a condensation reaction with an alcohol can be used as the component (b) of the present invention.

The component (c) of the present invention, the Zunawara chain extender, contains two or more active hydrogen-containing groups such as low molecular weight (less than 500 molecular weight) diols, triols, diamines, i-diamino, hydroxyalkylamines, etc. The following compounds can be used. Examples of chain extenders that can be used in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 2,2,4-trimethylbentanediol, and neopentyl glycol. ,
Alkylene oxide adduct of 1 bisfunol△ to hydrogenated bisphenol, glycerin, trimethyol-ethane, trimethylolbutylene [1 pan, ethylene diamine,
Propylene diamine, hexamethylene diamine, isoborone diamine, diaminocyclohexane, dicyclohexylmethane diamine, xylylene diamine, diethylene triamine, heptanoethanolamine, jetanolamine, triethanolamine, propatoolamine, dibrobanolamine, methyl jetanolamine etc. can be mentioned.

The (d) alkyl ketene dimer used in the present invention is
-Maximum % It is a compound represented by the formula % (where R and R' are alkyl groups) and is known as a fatty m derivative. Particularly preferred in the present invention is the use of argyl ketene dimers in which R and R' are alkyl groups having 8 or more carbon atoms in the above-mentioned maximum.

Since the alkyl ketene dimer easily reacts with an active hydrogen-containing compound to produce a ketocarboxylic acid derivative, it can be reacted with the aforementioned component (b) or (c) in the cylinder. Furthermore, when the terminal group of the urethane-based polymer or prepolymer obtained by the reaction of components (a), (b), and (c) above has active hydrogen, such polymer or prepolymer may be reacted with an alkyl ketene dimer. You can also do it.

When implementing the present invention, the above-mentioned (a), (b),
(c) Each component is mixed according to a conventional method for urethanization reaction, in the presence or absence of an inert solvent, using or not using an appropriate amount of a known urethanization reaction catalyst, at room temperature to 150°C, preferably. Component (d) is added and reacted at any point in the reaction process at a temperature of 50 to 120°C. However, component (d) can be reacted in advance with a part of components (b) and/or (c) prior to the urethanization reaction, or can be reacted with component (d) during or after the urethanization reaction. The reaction amount of alkyl ketene dimer is (a), (b), (c)
A suitable amount is about 0.1 to 5 mm%, particularly preferably a range of 0.5 to 2% by weight, based on the total type I of the reaction components. If it is less than 0.11 m5, the effect of the present invention will not be fully exhibited, and it will be difficult to obtain a urethane-based polymer with good adhesion to polypropylene film.
On the other hand, if it exceeds 5%, the chain extender of the urethane polymer will be inhibited, and the molecular weight of the urethane polymer will decrease, leading to the possibility that the strength properties of the coating composition will be poor.

In the method for producing a polyurethane resin of the present invention having the above-mentioned structure, the final product of the resin has a weight average molecular elevation of about 10,000 to 100,000, particularly preferably 20,000 to 70,000.
It is desirable to adjust the functional groups of each reaction component and to select reaction conditions so that the reaction conditions are within a range of 1,000,000.

[For production] The method for producing a polyurethane resin of the present invention includes Al.

An alkyl ketocarboxylic acid residue can be introduced by reacting a kyl ketene dimer.
This makes it easy to modify urethane polymers by introducing alkyl groups by utilizing the reactivity of argyl ketene dimers.

According to the method of the present invention, since higher alkyl groups can be easily introduced, the polyurethane resin obtained by the present invention has an increased affinity for aliphatic hydrocarbons, and has a higher affinity for polypropylene films. It is thought that it can exhibit excellent adhesive properties even if

[Examples] Hereinafter, the method for producing a polyurethane resin of the present invention will be described in more detail based on Examples and Test Examples.

Example 1 200 ffl 1 part of polyester diol with average molecular weight ffl 2000 obtained by the synthesis reaction of 1.4-butanediol and adipic acid, stearyl ketene dimer C16H33-CH=C-CI-1-C161133
0-C・=0 (Product name “Obel” Nippon Kika Co., Ltd. ￥f!J)
2.8 parts by weight and 17.5 parts by weight of ethyl acetate were charged into a reactor, heated in a nitrogen atmosphere, and reacted at 90 to 100°C for 30 minutes. Then isophone a diisocyanate 44
．． After the quadruple ID portion was added dropwise over 30 minutes, the mixture was allowed to react at the same temperature for 5 hours. After diluting this with ethyl acetate and cooling it to room temperature,
An isopropyl alcohol solution of a chain extender containing 1.62 parts of 1,4-butanediol was added dropwise, followed by reaction at 65-75°C for 4 hours.

The obtained polyurethane resin solution [A] has a nonvolatile content of 3
8.0%, viscosity 400 cps/25°C, average molecular weight (Mw) by GPC of Borisdylene standard is 2
It was 4800.

Example 2 A fiber using stearyl ketene dimer was operated in the same manner as in Example 1 except that the hanging part was 5.61%, and the nonvolatile content was 38.3%.
%, viscosity 330CI) S/ 25℃, M W 2300
0 polyurethane resin solution [[3] was obtained.

Comparative Example 1 Non-volatile content was 37.8%, viscosity was 4t5c, except that stearyl ketene dimer was not used, and all other operations were performed in the same manner as in Example 1.
A polyurethane resin solution [X] having a temperature of ps/25° C. and a M w of 26,500 was obtained.

Example 3 Polycarbonate with an average molecular fi of 2000 [Corac I-nediol (trade name: Plaxel L-2208, manufactured by Daicel Chemical T-Gyo Co., Ltd.) 200 weight ω parts, stearyl ketene dimer 2.8 parts, ethyl acetate 17 Charge 1 part of .5 layers into a reactor, heat under nitrogen atmosphere, and reduce to 90 to 100
The reaction was carried out at ℃ for 30 minutes. Next, 1-44.4 parts by weight of isophorone diisocyanate was added dropwise, and the mixture was reacted at the same temperature for 5 hours. This was diluted with ebul acetate, cooled to room temperature, and then the chain extender, isobutyl, containing 14.4 parts of isophoronediamine and 0,9-i [fi parts of 1,4-butanediol] was added. Pyl alcohol solution was added dropwise, followed by reaction at 65-75°C for 4 hours.

The obtained polyurethane resin solution [C] has a nonvolatile content of 37
．． 5%, viscosity 15.5 pS/25°C, MW 34000
Met.

Comparative Example 2 Non-volatile content was 37.4%, viscosity was 16.2, except that stearyl ketene dimer was not used, and all other operations were performed in the same manner as in Example 3.
A polyurethane resin solution [Y] of ps/25° C. and lvl w 35100 was obtained.

Example 4 Stearyl ketene dimer 266i ffi all,
Trimedyroll L1 pan 67 parts and ethyl acetate 5
0 parts by weight was charged into a reactor and reacted at 90 to 100°C for 1 hour to prepare an addition reaction product.

In a separate reactor, 4 parts by weight of the above addition reaction product, 20 Offl ffi parts of the polyester diol used in Example 1, and 17 parts by weight of ethyl acetate were charged and uniformly mixed by heating under a nitrogen atmosphere. Next, isophorone diisocyanate 1~
44.4 parts of heavy stones were added dropwise and reacted at 90 to 100°C for 5 parts. This was diluted with ethyl acetate, and an isopropyl alcohol solution of a chain extender containing 13.94 parts by weight of isoborone diamine and 1.17 parts by weight of 1,4-butanediol was subjected to W4F, and then 65 to The reaction was carried out at 75°C for 4 hours.

1q of polyurethane resin solution [I)] has a non-volatile content of 3
1.6%, viscosity 150cps/25℃, MW 250
It was 00.

[Test Example] Using each of the polyurethane resin solutions obtained in Examples and Comparative Examples as a vehicle component, a coating composition was obtained according to the following formulation.

Medium pigment (T i 02 ) 3o4r
Part A (ii) Resin 14
1 part (decoy, solvent, isopropanol, 14 parts, ethyl acetate, 42,000 parts) (mixed for 30 minutes using a paint shaker). ) and after leaving it for one day, the paste coating was evaluated in the following test.

(b) Adhesive cellophane adhesive tape was pasted on the paint film, forcefully peeled off, and the state of peeling between the forest wood film and the paint film was observed and evaluated using the following criteria.

O: Almost no peeling).

Part of ΔD peels off.

X: peels off almost completely.

The 60° gloss of the coating film on IC gloss-treated Boria [1 pyrene film (opp) was measured using a τ gloss meter.

Regarding the coating film of VNI Rocking OPP-T-, the blocking resistance of both the 7th side and the front/back side was measured at 50°C, 60%RH, 1kg/d.
, tested under 3-hour conditions and evaluated on a 5-point scale [5 (good) to 1].
(Bad) I did 1.

The binding is shown in Table 1.

Table 1 Polyurethane 1 @ Gloss 1) Gloss
Blocking Resistant Resin Cutting, Hi-E Machining M-4F
ii iTi/1 [A1 0 0005.9
3 5CBJOOOO○ 6.435 [C] Δ~00005.22~35 [D]
Oooog, oa 5 [XJ x
OOΔ 4.42-3 51) OPP: Treated boria 0 pyrene film PET: Polyester film NY: Nylon film CE: Cellophane [Effects of the invention] The method for producing a polyurethane resin of the present invention is a known production process for polyurethane resins. Moreover, the polyurethane resin obtained by the present invention exhibits an extremely useful effect industrially in that it exhibits good adhesion to various plastic boot stick molded products.

Therefore, if the polyurethane resin obtained according to the present invention is used as a vehicle component of paint or printing ink, or as an adhesive component, it is possible to further improve the quality of the coating composition.

Applicant: Seiko Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. In a method for producing a polyurethane resin by reacting (a) an organic polyisocyanate compound, (b) a polymeric polyol compound, and (c) a chain extender, at any stage of the above reaction, ( d) A method for producing a polyurethane resin, which comprises reacting an alkyl ketene dimer. 2. The method for producing a polyurethane resin according to claim 1, wherein an alkyl ketene dimer whose alkyl group has 8 or more carbon atoms is used. 3. The method for producing a polyurethane resin according to claim 2, wherein the alkyl ketene dimer (d) is a stearyl ketene dimer. 4. The method for producing a polyurethane resin according to claim 1, wherein (d) the alkyl ketene dimer is reacted with (b) the polymeric polyol compound in advance. 5. The method for producing a polyurethane resin according to claim 1, wherein (d) the alkyl ketene dimer is reacted with (c) the chain extender in advance.