JP5375542B2 - Polyurethane production catalyst and polyurethane production method - Google Patents

Description

  The present invention relates to a catalyst for producing a polyurethane by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a foam stabilizer, a crosslinking agent, and the like, and a polyurethane resin using the catalyst. It relates to a manufacturing method.

  In particular, the catalyst of the present invention is expected to be used as a catalyst for producing flexible polyurethane foam.

  A polyurethane resin is produced by reacting a polyol, which is a main raw material, with an organic polyisocyanate and / or an isocyanate prepolymer in the presence of a catalyst and, if necessary, an antifoaming agent, a surfactant, a crosslinking agent, and a foaming agent. Yes. Polyurethane resin can form a resin having a cross-linked structure and is excellent in adhesion to substrates, flexibility, and weather resistance, so automobiles, architecture, home appliances, heavy anticorrosion, paints, elastomers, sealing agents, adhesives, etc. Widely used in applications.

  In the production of a polyurethane resin, a molding method is generally used in which raw materials such as polyol and polyisocyanate are mixed and then filled into a mold or applied to a substrate to cause reaction and curing. In recent years, it has been required to increase the reactivity for the purpose of improving productivity. However, if the reactivity is accelerated, the curing of the urethane resin starts immediately, so the raw material does not flow to every corner of the mold, resulting in molding failure, or the raw material is cured before being applied to the base material. The problem is likely to occur.

  In other words, by suppressing the initial reactivity, the usable life (pot life) of the mixed liquid is lengthened, the filling into the mold and the application to the base material are facilitated, and the rapid curability after a certain time elapses. There is a need for a so-called delayed catalyst that provides rapid curability by heat treatment after filling into a mold or after application to a substrate.

  As these polyurethane resin production catalysts, tertiary amine catalysts and metal catalysts are widely used. In particular, as catalysts used for non-foaming applications such as coatings, adhesives, sealants and elastomers, metal catalysts such as lead catalysts and organotin catalysts are often used because of their high activity and urethane reaction. In many cases, mainly dibutyltin dilaurate (hereinafter sometimes referred to as DBTDL) or stannous octoate is frequently used (for example, see Patent Document 1).

  Since metal catalysts are generally highly toxic and it is difficult to obtain the desired reactivity, i.e., a retarding effect, the use of amine catalysts has been studied, and research on bicyclic tertiary amines has been actively conducted. However, many problems have been pointed out with respect to the bicyclic tertiary amine catalyst.

  For example, a bicyclic tertiary amine easily hydrolyzes in the presence of water, and thus has a problem of extremely low storage stability. Moreover, when it preserve | saves for a long time with the form (premix) which mixed the catalyst with the polyol, the foam stabilizer, etc., since there is water absorption, there exists a problem that storage stability is bad.

  In order to improve stability against hydrolyzability, bicyclic tertiary amines are mixed with organic acid blocking agents such as phenol, 2-ethylhexanoic acid and formic acid to form amine salt catalysts for urethane applications (See, for example, Patent Documents 4 to 8).

  However, when a phenolic salt of a bicyclic tertiary amine is used as a catalyst, the pot life at room temperature is long and a rapid curing is exhibited at a curing temperature of 40 ° C to 60 ° C. The stability of the catalyst was low, and there was a problem in long-term storage stability. Phenol is extremely toxic and falls under Article 18 of the Industrial Safety and Health Law and Enforcement Examples, and there is concern about its toxicity. When a phenolic salt of a bicyclic tertiary amine is used as a catalyst, there is a concern about the residual phenol in the urethane resin product, and therefore there is a strong demand for the development of an alternative blocking agent.

  In addition, when 2-ethylhexanoic acid, formic acid, or the like is used as a blocking agent for a bicyclic tertiary amine, the pot life at room temperature is long similarly to the phenol salt, and the pot temperature is rapidly increased at a curing temperature of 40 ° C to 60 ° C. Although it exhibits excellent curing and is superior in hydrolysis resistance to phenolic salts, there is a fatal defect that causes bubbles in the urethane resin due to carbon dioxide generated by reaction with polyisocyanate. In non-foamed urethane applications, the generation of bubbles becomes a defect in the final product, and therefore there is a strong demand for the development of a catalyst that does not generate bubbles.

  On the other hand, the applicant of the present invention provides an amine compound represented by the following general formula (1) as a catalyst composition capable of obtaining a polyurethane resin having almost no amine discharged from polyurethane products with good productivity and moldability, A patent application has already been filed for a catalyst composition for producing a polyurethane resin comprising an amine compound represented by general formula (2) or general formula (3) (see Patent Document 9).

［上記式（１）中、Ｒ_１及びＲ_２は各々独立して炭素原子数１〜４のアルキル基、ジメチルアミノプロピル基又はジエチルアミノプロピル基を表す。但し、Ｒ_１とＲ_２が直接又は窒素原子若しくは酸素原子を介在して結合した環状構造を表してもよい。Ｒ_３は炭素数２〜１６の直鎖又は分岐鎖のアルキル基を表す。Ｒ_４及びＲ_５は各々独立して炭素数２〜３の直鎖又は分岐鎖のアルキレン基を表す。ｍは０〜２の整数を表す。］

[In the above formula (1), R ₁ and R ₂ each independently represents an alkyl group having 1 to 4 carbon atoms, a dimethylaminopropyl group or a diethylaminopropyl group. However, R ₁ and R ₂ may represent a cyclic structure in which R ₁ and R ₂ are bonded directly or through a nitrogen atom or an oxygen atom. R ₃ represents a linear or branched alkyl group having 2 to 16 carbon atoms. R ₄ and R ₅ each independently represents a linear or branched alkylene group having 2 to 3 carbon atoms. m represents an integer of 0-2. ]

［上記式（２）中、Ｒ_６及びＲ_７は各々独立してメチル基又は下記一般式（ＩＶ）で示される置換基を表す。ｎ、ｐは１〜２の整数を表す。但し、Ｒ_６及びＲ_７が同時にメチル基になることはない。］
又は下記一般式（３）

[In the above formula (2), R ₆ and R ₇ each independently represent a methyl group or a substituent represented by the following general formula (IV). n and p represent an integer of 1 to 2. However, R ₆ and R ₇ are not simultaneously methyl groups. ]
Or the following general formula (3)

［上記式（３）中、Ｒ_６は下記一般式（４）で示される置換基を表す。ｎ、ｐは１〜２の整数を表す。］

[In the above formula (3), R ₆ represents a substituent represented by the following general formula (4). n and p represent an integer of 1 to 2. ]

［上記式（４）中、Ｒ_８は水素原子、又は炭素数１〜４のアルキル基を表す。ｑは１〜３の整数を表す。］
しかしながら、特許文献９に記載の触媒組成物は遅延性触媒ではなく、またこの触媒組成物を使用して製造される軟質ポリウレタンフォームは反発弾性が十分ではなく、その改善が望まれていた。

[In the formula (4), _{R 8} represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms. q represents an integer of 1 to 3. ]
However, the catalyst composition described in Patent Document 9 is not a retarding catalyst, and the flexible polyurethane foam produced using this catalyst composition does not have sufficient impact resilience, and an improvement thereof has been desired.

JP 11-279250 A Japanese Patent Laid-Open No. 2001-40258 JP 2001-72738 A JP 2002-3811 A JP 2003-137852 A JP 2003-140520 A JP-A-5-295074 Japanese Patent Laid-Open No. 9-52934 JP 2008-74903 A

  The present invention has been made in view of the above-mentioned background art, and its purpose is to delay the cream time without significantly changing the density, hardness and initial curing property of the polyurethane resin as compared with the conventional method. An object of the present invention is to provide a polyurethane resin production catalyst which is improved so that the reaction profile is initially delayed and the reaction proceeds rapidly in the latter half, and a polyurethane resin production method using the catalyst.

  As a result of intensive studies on an effective polyurethane retarding catalyst, the present inventor has found that a specific tertiary amine compound and a catalyst containing glycerin exhibit extremely effective retarding properties. It was found that by using the amine compound in combination, the resilience and hysteresis loss of the resulting foam were improved, and the present invention was completed.

  That is, the present invention is a polyurethane resin production catalyst and a polyurethane resin production method as described below.

  [1] Triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N′-tetramethylhexa Selected from the group consisting of methylenediamine, N-methyl-N ′-(2-dimethylaminoethyl) piperazine, dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, 1,2-dimethylimidazole, and mixtures thereof. A catalyst for producing a polyurethane resin comprising one or more tertiary amines (A) and one or more glycerols (C) selected from the group consisting of glycerol, diglycerol, and triglycerol.

  [2] Triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N′-tetramethylhexa Selected from the group consisting of methylenediamine, N-methyl-N ′-(2-dimethylaminoethyl) piperazine, dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, 1,2-dimethylimidazole, and mixtures thereof. One or more tertiary amines (A), the following general formula (1)

［上記式（１）中、Ｒ_１及びＲ_２は各々独立して炭素原子数１〜４のアルキル基、ジメチルアミノプロピル基又はジエチルアミノプロピル基を表す。但し、Ｒ_１とＲ_２が直接又は窒素原子若しくは酸素原子を介在して結合した環状構造を表してもよい。Ｒ_３は炭素原子数２〜１６の直鎖又は分岐鎖のアルキレン基を表す。Ｒ_４及びＲ_５は各々独立して炭素原子数２〜３の直鎖又は分岐鎖のアルキレン基を表す。ｍは０〜２の整数を表す。］
で示されるアミン化合物からなる群より選ばれる一種又は二種以上のアミン化合物（Ｂ）、並びにグリセリン、ジグリセリン、及びトリグリセリンからなる群より選ばれる一種又は二種以上のグリセリン類（Ｃ）を含有するポリウレタン樹脂製造用触媒。

[In the above formula (1), R ₁ and R ₂ each independently represents an alkyl group having 1 to 4 carbon atoms, a dimethylaminopropyl group or a diethylaminopropyl group. However, R ₁ and R ₂ may represent a cyclic structure in which R ₁ and R ₂ are bonded directly or through a nitrogen atom or an oxygen atom. R ₃ represents a linear or branched alkylene group having 2 to 16 carbon atoms. R ₄ and R ₅ each independently represents a linear or branched alkylene group having 2 to 3 carbon atoms. m represents an integer of 0-2. ]
1 type or 2 or more types of amine compounds (B) selected from the group consisting of the amine compounds represented by the above, and 1 type or 2 or more types of glycerols (C) selected from the group consisting of glycerin, diglycerin, and triglycerin. A catalyst for producing a polyurethane resin.

  [3] The amine compound (B) is N, N-dimethyl-N ′, N′-bis (hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) propanediamine, N , N-dimethyl-N ′, N′-bis (hydroxyethyl) neopentanediamine, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) hexanediamine, N- (N, N-bis (hydroxy) Ethyl) aminoethyl) piperidine, N, N-bis (dimethylaminopropyl) -N ′, N′-bis (hydroxyethyl) ethylenediamine, N, N-bis (dimethylaminopropyl) -N ′, N′-bis ( Hydroxyethyl) propanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) ethylenediamine, N, N-dimethyl N ′, N′-bis (2-hydroxypropyl) propanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) neopentanediamine, N, N-dimethyl-N ′, N ′ -Bis (2-hydroxypropyl) hexanediamine, N- (N, N-bis (hydroxyethyl) aminoethyl) piperidine, N, N-bis (dimethylaminopropyl) -N ', N'-bis (hydroxyethyl) It is selected from the group consisting of ethylenediamine and N, N-bis (dimethylaminopropyl) -N ′, N′-bis (hydroxyethyl) propanediamine, for producing a polyurethane resin as described in [2] above catalyst.

  [4] The polyurethane resin according to any one of the above [1] to [3], wherein the tertiary amine (A) is contained in an amount of 10 to 40% by weight based on the whole catalyst for producing a polyurethane resin. Catalyst for production.

  [5] A method for producing a polyurethane resin, comprising reacting a polyol and an organic polyisocyanate in the presence of the polyurethane resin production catalyst according to any one of [1] to [4].

  [6] A process for producing a flexible polyurethane foam, comprising reacting a polyol and an organic polyisocyanate in the presence of the catalyst for producing a polyurethane resin according to any one of [1] to [4] above and a foaming agent. .

  Since the initial activity of the catalyst for producing a polyurethane resin of the present invention is weak, the time from when the raw material polyol and the organic isocyanate are mixed to when the foam formation reaction is started can be extended. As a result, it is possible to improve the operability and liquid flowability of the mixed liquid, such as allowing the raw material liquid to flow sufficiently to every corner of the large mold.

  The catalyst for producing a polyurethane resin of the present invention exhibits catalytic activity when the foam formation reaction proceeds and the reaction temperature rises. As a result, the catalytic activity is remarkably increased, and the foam formed by the urethane reaction is allowed to flow into the complex mold without being thinned. For this reason, a polyurethane foam in which the foam density is distributed in a well-balanced manner from the center to the skin and the skin is firm is obtained.

  In addition, since a normal retarding catalyst contains an acid blocking agent, there is a concern about corrosiveness to metal materials. However, since the retarding catalyst of the present invention does not contain an acid blocking agent, it is corrosive to metal materials. It does not violate polyurethane manufacturing equipment such as catalyst storage tanks and foaming equipment, and helps to improve productivity.

  Furthermore, when the catalyst for producing a polyurethane resin of the present invention containing the amine compound (B) is used, the resilience and hysteresis loss of the resulting foam are better than when not used.

  The present invention is described in detail below.

  The first polyurethane resin production catalyst of the present invention is triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N , N ′, N′-tetramethylhexamethylenediamine, N-methyl-N ′-(2-dimethylaminoethyl) piperazine, dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, 1,2-dimethylimidazole, And one or more tertiary amines (A) selected from the group consisting of these and mixtures thereof, and one or more glycerols (C) selected from the group consisting of glycerin, diglycerin, and triglycerin (C ).

  The second polyurethane resin production catalyst of the present invention comprises the above tertiary amines (A) and the following general formula (1).

［上記式（１）中、Ｒ_１及びＲ_２は各々独立して炭素原子数１〜４のアルキル基、ジメチルアミノプロピル基又はジエチルアミノプロピル基を表す。但し、Ｒ_１とＲ_２が直接又は窒素原子若しくは酸素原子を介在して結合した環状構造を表してもよい。Ｒ_３は炭素原子数２〜１６の直鎖又は分岐鎖のアルキレン基を表す。Ｒ_４及びＲ_５は各々独立して炭素原子数２〜３の直鎖又は分岐鎖のアルキレン基を表す。ｍは０〜２の整数を表す。］
で示されるアミン化合物からなる群より選ばれる一種又は二種以上のアミン化合物（Ｂ）、並びに上記グリセリン類（Ｃ）を含有することを特徴とする。

[In the above formula (1), R ₁ and R ₂ each independently represents an alkyl group having 1 to 4 carbon atoms, a dimethylaminopropyl group or a diethylaminopropyl group. However, R ₁ and R ₂ may represent a cyclic structure in which R ₁ and R ₂ are bonded directly or through a nitrogen atom or an oxygen atom. R ₃ represents a linear or branched alkylene group having 2 to 16 carbon atoms. R ₄ and R ₅ each independently represents a linear or branched alkylene group having 2 to 3 carbon atoms. m represents an integer of 0-2. ]
1 type or 2 or more types of amine compounds (B) chosen from the group which consists of amine compounds shown by these, and the said glycerol (C), It is characterized by the above-mentioned.

  The amine compound represented by the general formula (1) is, for example, a tertiary amine compound having two or more hydroxyalkyl groups, and 2 to 6 mol of ethylene oxide or propylene oxide is added to the primary amino group of the corresponding amine compound. It is obtained by addition reaction. The added mole number of ethylene oxide or propylene oxide is preferably 2 moles from the viewpoint of catalytic activity.

  Examples of the amine compound represented by the general formula (1) include N, N-dimethyl-N ′, N′-bis (hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′, N′-bis (hydroxy). Ethyl) propanediamine, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) neopentanediamine, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) hexanediamine, N, N— Dimethyl-N ′, N′-bis (hydroxyethyl) hexadecyldiamine, N, N-diethyl-N ′, N′-bis (hydroxyethyl) ethylenediamine, N, N-diethyl-N ′, N′-bis ( Hydroxyethyl) propanediamine, 4-bis (hydroxyethyl) amino-1-diethylaminopentane, N, N-diethyl-N ′, N′-bis Hydroxyethyl) hexanediamine, N- (N, N-bis (hydroxyethyl) aminoethyl) piperidine, N- (N, N-bis (hydroxyethyl) aminoethyl) -N′-methylpiperazine, N- (N, N-bis (hydroxyethyl) aminopropyl) piperidine, N- (N, N-bis (hydroxyethyl) aminopropyl) -N′-methylpiperazine, N, N-bis (dimethylaminopropyl) -N ′, N ′ -Bis (hydroxyethyl) ethylenediamine, N, N-bis (dimethylaminopropyl) -N ', N'-bis (hydroxyethyl) propanediamine, N, N-bis (diethylaminopropyl) -N', N'-bis (Hydroxyethyl) propanediamine, N, N-dimethyl-N′N′-bis (2-hydroxypropyl) Tylenediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) propanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) neopentanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) hexanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) hexadecyldiamine, N, N-diethyl-N ', N'-bis (2-hydroxypropyl) ethylenediamine, N, N-diethyl-N', N'-bis (2-hydroxypropyl) propanediamine, 4-bis (2-hydroxypropyl) amino-1-diethylamino Pentane, N, N-diethyl-N ′, N′-bis (2-hydroxypropyl) hexanediamine, N- (N, N-bis (2-H (Droxypropyl) aminoethyl) piperidine, N- (N, N-bis (2-hydroxypropyl) aminoethyl) -N′-methylpiperazine, N- (N, N-bis (2-hydroxypropyl) aminopropyl) Piperidine, N- (N, N-bis (2-hydroxypropyl) aminopropyl) -N′-methylpiperazine, N, N-bis (dimethylaminopropyl) -N ′, N′-bis (2-hydroxypropyl) Ethylenediamine, N, N-bis (dimethylaminopropyl) -N ′, N′-bis (2-hydroxypropyl) propanediamine, N, N-bis (diethylaminopropyl) -N ′, N′-bis (2-hydroxy) Propyl) propanediamine and the like.

  Of these, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) propane are particularly preferred because of their high catalytic activity. Diamine, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) neopentanediamine, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) hexanediamine, N- (N, N— Bis (hydroxyethyl) aminoethyl) piperidine, N, N-bis (dimethylaminopropyl) -N ′, N′-bis (hydroxyethyl) ethylenediamine, N, N-bis (dimethylaminopropyl) -N ′, N ′ -Bis (hydroxyethyl) propanediamine, N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) ethylenediamine N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) propanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) neopentanediamine, N, N— Dimethyl-N ′, N′-bis (2-hydroxypropyl) hexanediamine, N- (N, N-bis (hydroxyethyl) aminoethyl) piperidine, N, N-bis (dimethylaminopropyl) -N ′, N '-Bis (hydroxyethyl) ethylenediamine, N, N-bis (dimethylaminopropyl) -N', N'-bis (hydroxyethyl) propanediamine.

  The content ratio of the glycerol solvent and the tertiary amine used in the catalyst of the present invention is 1 to 70%, preferably 10 to 40% by weight of the tertiary amine with respect to the whole catalyst. . The reason is that the cream time is further delayed.

  In the catalyst of the present invention, a catalyst other than the above-described tertiary amine (A) and amine compound (B) (hereinafter referred to as “other catalyst”) can be used in combination. Examples of other catalysts include conventionally known tertiary amines, quaternary ammonium salts, organometallic catalysts, carboxylic acid metal salts, and the like. However, since the organometallic catalyst has the above-mentioned problems, it is desirable to reduce the amount of use or not to use it. Moreover, it is not necessary to use the amine compound represented by the general formula (2) or the general formula (3) as the catalyst of the present invention.

  The tertiary amines may be conventionally known ones, and are not particularly limited. For example, trimethylamine, triethylamine, dimethylpropylamine, dimethyloctylamine, dimethyldodecylamine, dimethyltetradecylamine, dimethylhexadecylamine. N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N "-Pentamethyldipropylenetriamine, N, N, N ', N'-tetramethyloctamethylenediamine, N, N, N', N'-tetramethylundecamethylenediamine, N, N, N ', N' -Tetramethylguanidine, 1,5-diaza-bicyclo (4,3,0) nonene-5, 1,8-diazabi B [5.4.0] undecene-7, quinuclidine, 2-methyltriethylenediamine, N, N′-dimethylpiperazine, N-methyldicyclohexylamine, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethyl Morpholine, 1-methylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 2,4,6 -Tertiary amine compounds such as tris (dimethylaminomethyl) phenol.

  The quaternary ammonium salts may be those conventionally known and are not particularly limited. For example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide salts, and the like. And tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  The organometallic catalyst may be any conventionally known one, and is not particularly limited. For example, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diester Examples include acetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, and the like.

  The carboxylic acid metal salt is not particularly limited as long as it is a conventionally known metal salt, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. The carboxylic acid is not particularly limited, but examples thereof include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid. Etc. are mentioned as a suitable example. Suitable examples of the metal forming the carboxylate include alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as calcium and magnesium.

  Although the usage-amount of another catalyst is not specifically limited, It is desirable that it is 0-3 weight part with respect to 1 weight part of tertiary amine (A).

  The polyurethane resin production catalyst of the present invention can be used as a retarding catalyst for any of soft slab foam, soft mold foam, semi-rigid foam, integral skin foam, rigid foam, and polyurethane elastomer.

  The method for producing a polyurethane resin of the present invention is characterized in that a polyol and an organic polyisocyanate are reacted in the presence of the above-described catalyst for producing a polyurethane resin of the present invention.

  Moreover, the manufacturing method of the flexible polyurethane foam of this invention is characterized by making a polyol and organic polyisocyanate react in presence of the above-mentioned catalyst for polyurethane resin manufacture, and a foaming agent.

  As the polyol used in the production method of the present invention, conventionally known polyether polyols, polyester polyols, polymer polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols can be used. These polyols can be used alone or in combination as appropriate.

  Examples of the polyether polyol include compounds having at least two or more active hydrogen groups (for example, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol, amines such as ethylenediamine, ethanol, and the like. Examples include those obtained by adding an alkylene oxide typified by ethylene oxide or propylene oxide to a starting material such as alkanolamines such as amine and diethanolamine (for example, Gunter Oertel, “Polyurethane Handbook”, (See the method described in the 1985 edition, pages 42-53). Particularly preferred are those having a molecular weight of about 3000 to 12000 starting from glycerin.

  Examples of the polyester polyol include those obtained from the reaction of dibasic acid and glycol, polyesters derived from the treatment of nylon waste, TMP, pentaerythritol waste, phthalic polyester waste, waste Examples include polyols (for example, see Keiji Iwata, “Polyurethane Resin Handbook”, first edition, 1987, page 117).

  Examples of the polymer polyol include a polymer polyol obtained by reacting the above-described polyol and an ethylenically unsaturated monomer (eg, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst (eg, Gunter Oertel). (See, "Polyurethane Handbook", 1985 edition, pages 75-76). Particularly preferred as the polymer polyol is one having a molecular weight of about 5000 to 12000.

  The polyisocyanate used in the present invention may be a conventionally known organic polyisocyanate and is not particularly limited. For example, toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), naphthylene diisocyanate. , Aromatic polyisocyanates such as xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate, isophorone diisocyanate, and mixtures thereof. Examples of TDI and derivatives thereof include a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate or a terminal isocyanate prepolymer derivative of TDI. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenyl-polymethylene diisocyanate and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group.

  Of these, a mixture of TDI and MDI is particularly preferred in the production of flexible foam, and MDI is particularly preferred in the production of semi-rigid foam, integral skin foam and rigid foam.

  In the production method of the present invention, the isocyanate index [= (isocyanate group / active hydrogen group capable of reacting with isocyanate group) (molar ratio) × 100] is not particularly limited, but is not limited to flexible foam, semi-rigid foam, and integrator. In the manufacture of ruskin foam, it is generally in the range of 70 to 130, and in the manufacture of rigid foam and urethane elastomer, it is generally in the range of 70 to 250.

  In the production method of the present invention, a foaming agent can be used if necessary. Examples of the foaming agent include water and / or halogenated hydrocarbons. Examples of the halogenated hydrocarbon include conventionally known halogenated methanes and halogenated ethanes. Specifically, methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, dichlorotrifluoromethane, dichloromonofluoromethane, and the like are used. be able to.

  A particularly preferred foaming agent is water, and the amount used thereof may vary depending on the density of the target polyurethane foam, but is usually 2 parts by weight or more, more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the polyol. Range.

  In the production method of the present invention, if necessary, a foam stabilizer can be used. As the foam stabilizer, for example, a conventionally known organosilicone surfactant is preferable, and the amount used is usually in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of polyol. .

  In the production method of the present invention, if necessary, a crosslinking agent or a chain extender can be used. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols (for example, ethylene glycol and 1,4-butanediol), low molecular weight amine polyols (for example, diethanolamine, triethanolamine, and the like), polyamines (for example, For example, ethylenediamine, xylylenediamine, methylenebisorthochloroaniline, etc.) can be used. Of these, diethanolamine and triethanolamine are preferred.

  Moreover, in the manufacturing method of this invention, a coloring agent, a flame retardant, an anti-aging agent, other well-known additives, etc. can be used as needed. The types and amounts of these additives can be used within the range normally used without departing from the known formats and procedures.

  Hereinafter, although demonstrated based on an Example and a comparative example, this invention is limited to only these Examples and is not interpreted.

  An example in which the catalyst of the present invention using glycerin and the catalyst using other low molecular weight polyhydric alcohol or low molecular weight amine polyol are compared is shown below.

Examples 1-2 and comparative examples 1-11.
A polyol, water, a crosslinking agent, and a foam stabilizer were mixed at the raw material blending ratio shown in Table 1 to prepare Premix A.

プレミックスＡ ７９．５ｇを３００ｍｌポリエチレンカップに取り、更に表２に示す触媒を、反応性が下記のゲルタイムで６０±１秒となる量添加し、２５℃に温度調整した。

79.5 g of Premix A was placed in a 300 ml polyethylene cup, and the catalyst shown in Table 2 was added in an amount such that the reactivity was 60 ± 1 seconds with the following gel time, and the temperature was adjusted to 25 ° C.

  In a separate container, the polyisocyanate liquid (MDI) whose temperature was adjusted to 25 ° C. was added in an amount such that the isocyanate index [= (active hydrogen group capable of reacting with isocyanate group / isocyanate group) (molar ratio) × 100] was 100. The mixture was placed in the cup containing the mix A and rapidly stirred at 6000 rpm for 5 seconds with a stirrer.

  The mixed and stirred liquid mixture was transferred to a 2 L polyethylene cup whose temperature was adjusted to 60 ° C., and the reactivity during foaming was measured.

Next, the raw material scale was increased and mixed in a mold (inner dimensions, made of aluminum of 25 × 25 × 8 cm) whose temperature was adjusted to 60 ° C. by the same operation so that the total density of the foam was 53 kg / m ^3. The solution was put in, covered and foamed. The foam was removed 8 minutes after the time when the mixed solution was added. From the molded foam, foam hardness, total foam density, core density, hysteresis loss and foam compression set were measured. The results are also shown in Table 2.

  The measurement method for each measurement item is as follows.

-Reactive measurement item Cream time: The foaming start time and the foam start time were measured visually.
Gel time: The time required for the reaction to progress to a resinous substance from a liquid substance was measured.
Rise time: The time when the rising of the foam stopped was measured with an infrared sensor.

  -Foam total density, core density: after curing the foam molded with a mold (inner dimensions, 25 x 25 x 8 cm made of aluminum) at 23 ° C x 7 days, the dimensions and weight were measured to determine the total density of the foam . Further, a foam of 21 × 21 × 6 cm size was sampled from this foam with a foam cutter, and the weight was measured to obtain the core density of the foam.

  -Hardness of the foam: After adjusting the state at 23 ° C x 16 hrs or more using the foam whose core density was determined, the hardness of the foam was measured. A compression jig (a disk having a diameter of 20 cm) was attached to a tensile tester (manufactured by A & D, product name: Tensilon RTM500), and a foam was set. As pre-compression, 300 mm / min. The disk was moved up and down at a speed of 2, and a compression operation corresponding to 40% of the foam thickness was performed twice. The hardness of the foam was measured by reading the compressive stress at 40% compression by the compression operation performed for the third time, and taking it as the hardness of the foam.

  Hysteresis loss: Hysteresis loss was measured as follows under a 23 ° C. atmosphere using a foam and a testing machine whose foam hardness was measured. As pre-compression, 100 mm / min. The disk was moved up and down at a speed of 1, and a compression operation corresponding to 65% of the foam thickness was performed once. Hysteresis loss measurement is the second compression operation, the stress strain curve during pressurization and the stress strain curve during depressurization are obtained, and from the stress strain curve during pressurization and decompression obtained by this operation Individual integral values are obtained, and hysteresis loss [= (integral value of stress-strain curve at pressurization−integral value of stress-strain curve at decompression) / integral value of stress-strain curve at pressurization × 100] is obtained. It was. The foam with less hysteresis loss was judged to have high elasticity.

  Compression set: Four foams having dimensions of 5 × 5 × 2.5 cm were cut from the foam whose core density (hysteresis loss) was measured, and the thickness before the test was measured. In the test, in accordance with JIS K6401-1980, a compression jig was used to compress the foam under the conditions of 50% compression and 70 ° C. × 22 hrs, and subjected to accelerated deterioration treatment. After treatment, compression is released, and after adjusting the state at 23 ° C. for 30 minutes, the thickness of the foam is measured, and compression set (dry set: Dry-CS) [= (thickness before test−thickness after test) / test Previous thickness × 100] was determined.

  The reaction conditions and results of Examples 1 and 2 and Comparative Examples 1 to 11 are shown together in Table 2.

表２から明らかなように、実施例１、２において、本発明の触媒組成物を用いたポリウレタンフォームのクリームタイムは、比較例１〜１１の触媒組成物を用いたポリウレタンフォームのクリームタイムに比べ、７〜１０秒長くなっており、初期反応が顕著に遅延化したことがわかる。

As is clear from Table 2, in Examples 1 and 2, the cream time of the polyurethane foam using the catalyst composition of the present invention was compared with the cream time of the polyurethane foam using the catalyst composition of Comparative Examples 1-11. 7 to 10 seconds longer, indicating that the initial reaction was significantly delayed.

Examples 3-4 and Comparative Examples 12-13.
Using the catalysts shown in Table 3, the reactivity during foaming was measured in the same manner as in Examples 1 and 2 and Comparative Examples 1 to 11.

  The catalyst composition ratio, catalyst addition amount, and reactivity results are also shown in Table 3.

表３から明らかなように、実施例３、４において、本発明の触媒組成物を用いたポリウレタンフォームのクリームタイムは、比較例１２、１３の触媒組成物を用いたポリウレタンフォームのクリームタイムに比べ、５〜１０秒長くなっており、初期反応が顕著に遅延化したことがわかる。

As is clear from Table 3, in Examples 3 and 4, the cream time of the polyurethane foam using the catalyst composition of the present invention was compared with the cream time of the polyurethane foam using the catalyst composition of Comparative Examples 12 and 13. It is 5-10 seconds longer, indicating that the initial reaction has been significantly delayed.

Examples 5 to 7 and Comparative Example 14
The amount of triethylenediamine was kept constant, the amount of glycerol or the amount of dipropylene glycol was changed, and the reactivity during foaming was measured in the same manner as in Examples 1 and 2 and Comparative Examples 1 to 11. Examined.

触媒組成比、触媒添加量、及び反応性の結果を表４に併せて示す。

The catalyst composition ratio, catalyst addition amount, and reactivity results are also shown in Table 4.

  As is clear from Table 4, it was confirmed that the catalyst of the present invention has a delayed effect as the amount of glycerin increases.

  On the other hand, the catalyst of the comparative example showed almost no delay effect even when the amount of dipropylene glycol was increased.

Example 8 to Example 10 and Comparative Example 15
A polyol, water, a crosslinking agent, and a foam stabilizer were mixed at the raw material blending ratio shown in Table 5 to prepare a premix A ′.

プレミックスＡ’ ８６．２ｇを３００ｍｌポリエチレンカップに取り、更に表６に示す触媒を各々反応性が下記のゲルタイムで５６秒となる量を添加し２０℃に温度調整した。別容器で２０℃に温度調整したポリイソシアネート液（ＴＭ８０）をイソシアネートインデックス［＝（イソシアネート基／イソシアネート基と反応しうる活性水素基）（モル比）×１００］が１０５となる量だけプレミックスＡのカップの中に入れ、素早く攪拌機にて６０００ｒｐｍで５秒間攪拌した。混合攪拌した混合液を６０℃に温度調節した２Ｌポリエチレンカップに移し発泡中の反応性を測定した。

86.2 g of premix A ′ was placed in a 300 ml polyethylene cup, and the catalyst shown in Table 6 was added in an amount such that the reactivity was 56 seconds with the gel time shown below, and the temperature was adjusted to 20 ° C. Premix A for polyisocyanate liquid (TM80) whose temperature was adjusted to 20 ° C. in a separate container by an amount such that isocyanate index [= (active hydrogen group capable of reacting with isocyanate group / isocyanate group) (molar ratio) × 100] was 105 And rapidly stirred with a stirrer at 6000 rpm for 5 seconds. The mixed and stirred liquid mixture was transferred to a 2 L polyethylene cup whose temperature was adjusted to 60 ° C., and the reactivity during foaming was measured.

  Next, the raw material scale is increased, and the total density of the foam is 51.5 to 52 Kg / m 3 in a mold (inner dimensions, made of aluminum of 25 × 25 × 8 cm) whose temperature is adjusted to 60 ° C. by the same operation. The mixed solution was put in, covered and foamed. The foam was removed 10 minutes after the time when the mixed solution was added. From the molded foam, the hardness of the foam, the total density and density distribution of the foam, the core density, the hysteresis loss, the resilience, and the compression set of the foam were measured and compared. The results are shown in Table 6. In addition, the measuring method of each measurement item is as Example 1-2 and Comparative Examples 1-11, except the density distribution of a foam shown below, and a compression set.

  -Density distribution of foam: The foam molded with a mold (made of aluminum of 25 × 25 × 8 cm) was divided into five equal parts in the thickness direction, and the size and weight of each foam were measured to obtain the density. For the density distribution of the foam, find the difference between the density of the foam in the center and the density of the upper and lower foams, and further find the difference in the density difference between the upper and lower foams, and balance those with small differences from the center. The foam was judged to have a density distribution.

  ・ Determination of foam with a firm skin: Divide the foam molded in a mold (inner dimensions, 25 x 25 x 8 cm aluminum) into 5 equal parts in the thickness direction, measure the dimensions and weight of each foam, and determine the density. It was. The density of the foam in the center and the density difference between the upper and lower foams were determined, and the foam having a large difference was judged as a foam having a firm skin.

  Compression set: Four foams having dimensions of 5 × 5 × 2.5 cm are cut from the foam whose core density (hysteresis loss) is measured, and the thickness before the test is measured. In the test, in accordance with JIS K6401-1980, a compression jig was used to compress the foam under the conditions of 50% compression and 70 ° C. × 22 hrs, and subjected to accelerated deterioration treatment. After treatment, compression is released, and after adjusting the state at 23 ° C. for 30 minutes, the thickness of the foam is measured, and compression set (dry set: Dry-CS) [= (thickness before test−thickness after test) / test Previous thickness × 100] was determined. Similarly, using a compression jig, the foam was placed under the conditions of 50% compression, 50 ° C. × 22 hr, and 95% humidity for accelerated deterioration treatment. After the treatment, compression is released, and after adjusting the state at 23 ° C. × 30 minutes, the thickness of the foam is measured, and compression set (wet set: Wet-CS) [= (thickness before test−thickness after test) / test Previous thickness × 100] was determined.

  The reaction conditions and results of Example 8 and Comparative Example 15 are also shown in Table 6.

表６から明らかなように、実施例８〜実施例１０において、本発明の触媒組成物を用いたポリウレタンフォームのクリームタイムは、比較例１５の触媒組成物を用いたポリウレタンフォームのクリームタイムに比べ、３〜４秒長くなっており、初期反応が顕著に遅延化したことがわかる。

As is clear from Table 6, in Examples 8 to 10, the cream time of the polyurethane foam using the catalyst composition of the present invention was compared with the cream time of the polyurethane foam using the catalyst composition of Comparative Example 15. 3 to 4 seconds longer, indicating that the initial reaction was significantly delayed.

Further, in Examples 8 to 10, the difference between the upper skin density and the lower skin density was as small as 6.4 to 7.8 kg / m ^3, and the density increase was confirmed from the center to the skin in a well-balanced manner. Furthermore, a foam having a firm skin with a density difference between the center and the upper part of 12.9 to 14.1 kg / m ³ and a density difference of the lower part of 5.9 to 7.3 kg / m ³ was obtained.

On the other hand, in Comparative Example 15, since the difference between the upper skin density and the lower skin density was as large as 12.9 kg / m ³ , it was confirmed that the density distribution was unbalanced. Is 16.7 kg / m ³ , but the density difference at the bottom is as small as 3.8 kg / m ³ , indicating that the epidermis is not sufficiently formed.

  Furthermore, Example 9 and Example 10 are catalyst compositions containing N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) propanediamine corresponding to the amine compound (B). However, compared with Example 8 using the catalyst composition which does not contain N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) propanediamine, hysteresis loss and impact resilience were improved.

Claims (4)

Triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N′-tetramethylhexamethylenediamine, One or two selected from the group consisting of N-methyl-N ′-(2-dimethylaminoethyl) piperazine, dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, 1,2-dimethylimidazole, and mixtures thereof. Tertiary amines (A), N, N-dimethyl-N ′, N′-bis (hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′, N′-bis (hydroxyethyl) propanediamine N, N-dimethyl-N ′, N′-bis (hydroxyethyl) neopentanediamine, N, N-dimethyl-N ′, N′-bis ( Droxyethyl) hexanediamine, N- (N, N-bis (hydroxyethyl) aminoethyl) piperidine, N, N-bis (dimethylaminopropyl) -N ', N'-bis (hydroxyethyl) ethylenediamine, N, N- Bis (dimethylaminopropyl) -N ′, N′-bis (hydroxyethyl) propanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) ethylenediamine, N, N-dimethyl-N ′ , N′-bis (2-hydroxypropyl) propanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) neopentanediamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) hexanediamine, N- (N, N-bis (hydroxyethyl) aminoethyl) piperidine, N, N-bis ( Methyl aminopropyl) -N ', N'- bis (hydroxyethyl) ethylenediamine, and N, N- bis (dimethylaminopropyl) -N', is selected from the group consisting of N'- bis (hydroxyethyl) propanediamine A catalyst for producing a polyurethane resin comprising one or more amine compounds (B) and one or more glycerols (C) selected from the group consisting of glycerol, diglycerol and triglycerol. The catalyst for producing a polyurethane resin according to claim 1, wherein the tertiary amine (A) is contained in an amount of 10 to 40% by weight based on the whole catalyst for producing the polyurethane resin. A process for producing a polyurethane resin, comprising reacting a polyol and an organic polyisocyanate in the presence of the polyurethane resin production catalyst according to claim 1 . A method for producing a flexible polyurethane foam, comprising reacting a polyol and an organic polyisocyanate in the presence of the catalyst for producing a polyurethane resin according to claim 1 or 2 and a foaming agent.