JP2019084679A - Method of producing urethane-integrated foam molded article - Google Patents

Abstract

To provide an urethane-integrated foam molded article whose acetaldehyde content is low.SOLUTION: In a method of producing an urethane-integrated foam molded article of this invention, a resin skin material (1), a base material (2), and an urethane foam layer (3) sandwiched between the resin skin material and the base material are integrally molded using a mold, and the urethane foam layer (3) is composed of urethane foam obtained by reacting a polyol mixture (P) including a polyol component (A), a foaming agent (C), a catalyst (D), and an additive (E), and a polyisocyanate component (B). A period from a start of blending the polyol mixture (P) and the polyisocyanate component (B) to removal of the urethane-integrated foam molded article is 45-75 seconds. An acetaldehyde content measured from the molded urethane-integrated foam molded article is 67 μg/kg or less, and a density of the urethane foam layer (3) is 0.15-0.25 g/cm.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a urethane integral foam.

  In recent years, aldehydes such as formaldehyde (volatile organic compounds (VOCs)) are required to prevent the diffusion of these compounds as much as possible in the housing field because they cause sick house syndrome and the like. Such a situation is the same in a vehicle cabin such as a car, and it is necessary to take measures against VOC.

  As a urethane integral foam molded article in a vehicle interior, there is a three-layered vehicle instrumental panel having a urethane foam layer integrally molded between a resin-made skin material and a base material. Also in the instrumental panel for vehicles, measures against VOC are being considered, for example, the surface of the urethane foam layer side by covering the granular aldehyde scavenger which captures the VOC generated in the urethane foam layer with the sheet material of communicating cells There is known a technique (see Patent Document 1) for arranging the

  On the other hand, it comprises a sheet pad made of a flexible polyurethane foam coated on the surface with an aldehyde scavenger made of amines etc., and a flexible polyurethane foam made by injection molding a foamed urethane raw material added with the above aldehyde scavenger into a mold Seat pads are known. According to these pads, VOC generated in the pad can be captured by an aldehyde scavenger so as not to scatter outside, and health problems such as sick house syndrome and chemical hypersensitivity can be eliminated (patent document 2).

Unexamined-Japanese-Patent No. 2007-216506 JP, 2005-124743, A

However, in the methods of Patent Documents 1 and 2, although the diffusion of aldehyde can be suppressed to some extent, there is a problem that the content of aldehyde can not be reduced.
An object of the present invention is to provide a urethane integrated foam molded article having a low acetaldehyde content.

As a result of intensive studies to solve the above problems, the present inventors reached the invention shown below.
That is, the present invention is a method for producing a urethane integrated foam molded article in which a urethane foam layer (3) is integrally molded between a resin-made skin material (1) and a base material (2) using a mold, The foamed layer (3) is formed by reacting a polyol mixture (P) containing a polyol component (A), a blowing agent (C), a catalyst (D) and an additive (E) with a polyisocyanate component (B) It consists of a urethane foam, Polyol component (A) contains following polyether polyol (A1)-(A3) and the following polymer polyol (L), (L) is the following polymer in following polyether polyol (A4) A polymer polyol containing fine particles (A5), wherein the content of (A1) in (A) is 50 to 55% by weight based on the weight of (A), and the content of (A2) is (A) 20 based on the weight of 5% by weight, the content of (A3) is 3 to 7% by weight based on the weight of (A), and the content of (L) is 15 to 25% by weight based on the weight of (A); The content of the fine particles (A5) is 4 to 8% by weight based on the weight of (A), the catalyst (D) contains the following (D1-1) and (D1-2), and in (P) The total content of (D1-1) and (D1-2) is 0.1 to 1% by weight based on the weight of (A), and the additive (E) contains the following (E1) The content of (E1) in (P) is 0.01 to 10% by weight based on the weight of (A), and mixing of the polyol mixture (P) and the polyisocyanate component (B) is started. It takes 45 to 75 seconds to remove the urethane integrated foam and it is measured from the molded urethane integrated foam. That the content of acetaldehyde is not more than 67μg / kg, a density of the urethane foam layer (3) is a method for producing a urethane integrally foam molded article is 0.15~0.25g / cm ^3.
(A1): polyether having a number average functional group number of 2.5 to 3.5, a hydroxyl value of 31 to 40 (mg KOH / g), and a content of terminal oxyethylene units of 14 to 17% by weight Polyol (A2): The number average functional group number is 1.5 to 2.5, the hydroxyl value is 20 to 35 (mg KOH / g), and the content of terminal oxyethylene units is 8 to 12% by weight, Polyether polyol (A3) in which the total of oxyethylene units is 15 to 25% by weight: the number average functional group number is 2.5 to 3.5, the hydroxyl value is 250 to 310 (mg KOH / g), and the terminal Polyether polyol (A4) having a content of oxyethylene units of 5 to 15% by weight: The number average functional group number is 3.5 to 4.5, and the hydroxyl value is 20 to 30 (mg KOH / g), Terminal oxye Polyether polyol (A5): polymer fine particle polymer of vinyl monomer (b) having a content of ren units of more than 12% by weight and less than 15% by weight Polymer polyol (L): radical polymerization in polyether polyol (A4) A polymer polyol containing (A4) and polymer fine particles (A5) obtained by polymerizing a vinyl monomer (b) in the presence of an initiator, wherein the vinyl monomer (b) is acrylonitrile and styrene, (b Weight ratio of acrylonitrile to styrene (acrylonitrile / styrene) is 60/40 to 75/25, and the content of (A5) in (L) is 25 to 35 weight based on the weight of (L) % Polymer polyol catalyst (D1-1): N- (3-aminopropyl) -N, N ', N'-trimethyl-bis (2-aminoethyl) Ether catalyst (D1-2): N, N′-bis [3-dimethylaminopropyl] urea additive (E1): triazole

  According to the production method of the present invention, it is possible to obtain a urethane integrated foam having a low content of acetaldehyde.

The method for producing a urethane integrated foam molded article according to the present invention is a urethane integrated foam molded article in which a urethane foam layer (3) is integrally molded between a resin surface material (1) and a substrate (2) using a mold. A urethane foam layer (3) comprising a polyol mixture (P) containing a polyol component (A), a foaming agent (C), a catalyst (D) and an additive (E), and a polyisocyanate component It consists of a urethane foam formed by making it react with B), Polyol component (A) contains following polyether polyol (A1)-(A3) and the following polymer polyol (L), and (L) is the following polyether polyol (A4) contains a polymer polyol containing the following polymer fine particles (A5), and the content of (A1) in (A) is 50 to 55% by weight based on the weight of (A), (A2 Content of (A) 20 to 25% by weight based on the weight of (A3), 3 to 7% by weight based on the weight of (A), and 15 to 25% of the content of (L) based on the weight of (A) The content of the polymer fine particles (A5) is 4 to 8% by weight based on the weight of (A), and the catalyst (D) contains the following (D1-1) and (D1-2) And the total content of (D1-1) and (D1-2) in (P) is 0.1 to 1% by weight based on the weight of (A), and the additive (E) is the following (E1) And the content of (E1) in (P) is 0.01 to 10% by weight based on the weight of (A), the polyol mixture (P) and the polyisocyanate component (B) And 45 to 75 seconds from the start of mixing to the removal of the urethane unitary molded foam from molded urethane resin Integral content of acetaldehyde measured from molded foam is not more than 67μg / kg, urethane foam layer (3) METHOD density urethane integrally foam molded article is 0.15~0.25g / cm ³ of is there.
(A1): polyether having a number average functional group number of 2.5 to 3.5, a hydroxyl value of 31 to 40 (mg KOH / g), and a content of terminal oxyethylene units of 14 to 17% by weight Polyol (A2): The number average functional group number is 1.5 to 2.5, the hydroxyl value is 20 to 35 (mg KOH / g), and the content of terminal oxyethylene units is 8 to 12% by weight, Polyether polyol (A3) in which the total of oxyethylene units is 15 to 25% by weight: the number average functional group number is 2.5 to 3.5, the hydroxyl value is 250 to 310 (mg KOH / g), and the terminal Polyether polyol (A4) having a content of oxyethylene units of 5 to 15% by weight: The number average functional group number is 3.5 to 4.5, and the hydroxyl value is 20 to 30 (mg KOH / g), Terminal oxye Polyether polyol (A5): polymer fine particle polymer of vinyl monomer (b) having a content of ren units of more than 12% by weight and less than 15% by weight Polymer polyol (L): radical polymerization in polyether polyol (A4) A polymer polyol containing (A4) and polymer fine particles (A5) obtained by polymerizing a vinyl monomer (b) in the presence of an initiator, wherein the vinyl monomer (b) is acrylonitrile and styrene, (b Weight ratio of acrylonitrile to styrene (acrylonitrile / styrene) is 60/40 to 75/25, and the content of (A5) in (L) is 25 to 35 weight based on the weight of (L) % Polymer polyol catalyst (D1-1): N- (3-aminopropyl) -N, N ', N'-trimethyl-bis (2-aminoethyl) Ether catalyst (D1-2): N, N′-bis [3-dimethylaminopropyl] urea additive (E1): triazole

In the resin skin material (1), the resin skin material and the molding method thereof are not particularly limited as long as they can be used as an interior material for automobiles, but from the viewpoint of moldability and workability, a thermoplastic resin is slushed It is preferable to be molded by molding.
Examples of the thermoplastic resin include vinyl chloride resin, urethane (urea) resin, acrylic resin, ABS resin, polyamide, polyester, polycarbonate, polyethylene, polypropylene, polystyrene, and a mixture of two or more of these, and the like.
Among these, vinyl chloride resin and urethane (urea) resin are preferable from the viewpoint of soft feeling of the slush molded product, and urethane (urea) resin is particularly preferable.
In addition, urethane (urea) resin means urethane resin and / or urethane urea resin.

  Examples of the substrate (2) include polypropylene and glass fiber reinforced acrylonitrile / styrene copolymer resin.

The urethane foam layer (3) is obtained by reacting a polyol mixture (P) containing a polyol component (A), a foaming agent (C), a catalyst (D) and an additive (E) with a polyisocyanate component (B) It consists of urethane foam.
The polyol component (A) contains the following polyether polyols (A1) to (A3) and a polymer polyol (L).
(A1): polyether having a number average functional group number of 2.5 to 3.5, a hydroxyl value of 31 to 40 (mg KOH / g), and a content of terminal oxyethylene units of 14 to 17% by weight Polyol (A2): The number average functional group number is 1.5 to 2.5, the hydroxyl value is 20 to 35 (mg KOH / g), and the content of terminal oxyethylene units is 8 to 12% by weight, Polyether polyol (A3) in which the total of oxyethylene units is 15 to 25% by weight: the number average functional group number is 2.5 to 3.5, the hydroxyl value is 250 to 310 (mg KOH / g), and the terminal Polyether polyol (A4) having a content of oxyethylene units of 5 to 15% by weight: The number average functional group number is 3.5 to 4.5, and the hydroxyl value is 20 to 30 (mg KOH / g), Terminal oxye Polyether polyol (A5): polymer fine particle polymer of vinyl monomer (b) having a content of ren units of more than 12% by weight and less than 15% by weight Polymer polyol (L): radical polymerization in polyether polyol (A4) A polymer polyol containing (A4) and polymer fine particles (A5) obtained by polymerizing a vinyl monomer (b) in the presence of an initiator, wherein the vinyl monomer (b) is acrylonitrile and styrene, (b Weight ratio of acrylonitrile to styrene (acrylonitrile / styrene) is 60/40 to 75/25, and the content of (A5) in (L) is 25 to 35 weight based on the weight of (L) % Polymer polyol

  Examples of the polyether polyols (A1) to (A4) include compounds having a structure in which an alkylene oxide (hereinafter abbreviated as AO) is added to an active hydrogen-containing compound (a).

  As the active hydrogen-containing compound (a), monohydric or divalent or higher alcohol (a1), monohydric or higher phenol (a2), amine (a3), polycarboxylic acid (a4) and phosphoric acid (a5) Is included.

The monohydric or dihydric or higher alcohol (a1) includes a monohydric alcohol having 1 to 20 carbon atoms, a dihydric alcohol having 2 to 20 carbon atoms, a trihydric alcohol having 3 to 20 carbon atoms, and 5 to 20 carbon atoms 4 to 8 polyhydric alcohols are included.
As C1-C20 monohydric alcohol, linear or branched aliphatic monool, alicyclic monool, etc. are contained. As linear or branched aliphatic monools, methanol, ethanol, n-propanol, 2-propanol and the like can be mentioned. Cycloaliphatic monools include cycloalkylene monools and the like, and specific examples include cyclohexanol and cyclohexane methanol.
As C2-C20 dihydric alcohol, linear or branched aliphatic diol, alicyclic diol, etc. are contained. The linear or branched aliphatic diols include, for example, alkylene glycols, specifically ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3- and 1,4-butanediol, 1 , 6-hexanediol, neopentyl glycol and the like. Cycloaliphatic diols include, for example, cycloalkylene glycols, and specific examples include cyclohexanediol and cyclohexanedimethanol.
Examples of trihydric alcohols having 3 to 20 carbon atoms include aliphatic triols and the like. Aliphatic triols include alkanetriols and the like, and specific examples include glycerin, trimethylolpropane, trimethylolethane and hexanetriol.
Aliphatic polyols and saccharides are included as C4-C20 4- to 8-hydric polyhydric alcohols. Aliphatic polyols include alkane polyols and the like, and specific examples include pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin and dipentaerythritol. The aliphatic polyols also include intramolecular dehydrated products of alkanetriols and alkane polyols, and intermolecular dehydrated products of alkanetriols and / or alkane polyols. Specific examples of saccharides include sucrose, glucose, mannose, fructose, methyl glucoside and the like, and derivatives thereof are also included.

The monohydric or divalent or higher phenol (a2) includes phenol and polyhydric (di- to octahydric) phenol.
The polyhydric phenol includes single ring polyhydric phenol, bisphenol, a condensate of phenol and formaldehyde (novolak), polyphenol, a combination of two or more of them, and the like.
Examples of single ring polyhydric phenols include pyrogallol, hydroquinone and phloroglucin. Examples of bisphenols include bisphenol A, bisphenol F and bisphenol sulfone. Examples of polyphenols include those described in US Pat. No. 3,265,641.

The amine (a3) includes one having 2 to 8 active hydrogens, and includes ammonia, linear or branched aliphatic amines, aromatic amines, alicyclic amines and heterocyclic amines.
As linear or branched aliphatic amines, alkanolamines having 2 to 20 carbon atoms (such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine and aminoethylethanolamine), alkylamines having 1 to 20 carbon atoms (n- Butylamine and octylamine etc.), alkylene diamines of 2 to 6 carbon atoms (ethylene diamine, propylene diamine and hexamethylene diamine etc.) and polyalkylene polyamines of 4 to 20 carbon atoms (alkylene group having 2 to 6 carbon atoms, etc.) Specifically, diethylenetriamine, triethylenetetramine and the like can be mentioned.
As an aromatic amine, C6-C20 aromatic mono- or polyamines (Aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, diphenylether diamine etc.) etc. are mentioned.
As an alicyclic amine, a C4-C20 alicyclic amine (Isophorone diamine, cyclohexylene diamine, dicyclohexyl methane diamine etc.) etc. are mentioned.
As a heterocyclic amine, C4-C20 heterocyclic amines (a piperazine, an aminoethyl piperazine, the thing as described in Japanese Patent Publication No.55-21044 etc.) etc. are mentioned.

  Examples of the polycarboxylic acid (a4) include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.) and aromatic polycarboxylic acids having 8 to 18 carbon atoms Phthalic acid, terephthalic acid, isophthalic acid and trimellitic acid etc. can be mentioned.

Two or more of these active hydrogen-containing compounds may be used in combination.
Among these, monohydric or dihydric or higher alcohols (a1) are preferable from the viewpoint of curability and mechanical properties of urethane foam.

As AO to be added to the active hydrogen-containing compound (a), it is preferable to use AO composed of 1,2-AO having 3 or more carbon atoms and ethylene oxide (hereinafter abbreviated as EO).
Examples of 1,2-AO having 3 or more carbon atoms include 1,2-propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide and styrene oxide. From the viewpoint of productivity, PO is preferable as the 1,2-AO having 3 or more carbon atoms.

AO is preferably composed of only 1,2-AO with a carbon number of 3 or more and EO, but addition with other AO combined in the range of 10 wt% or less (more preferably 5 wt% or less) in AO It may be a thing.
Other AOs include 1,3-AO and 1,4-AO other than 1,2-AO having 3 or more carbon atoms, and specifically, those having 4 to 8 carbon atoms (1,3 -A butylene oxide, a 1, 4- butylene oxide, a 2, 3- butylene oxide etc. are mentioned.
These may be used alone or in combination of two or more.

  The addition method of AO may be either block addition or random addition, but it is preferable that at least the active hydrogen end of the polyether polyol is block addition.

  As a catalyst used at the time of AO addition, in addition to alkaline catalysts (such as KOH and CsOH), catalysts described in JP-A 2000-344881 [Tris (pentafluorophenyl) borane etc.], JP-A-11-120300 The catalyst (magnesium perchlorate etc.) may be used (the same applies to the following AO adducts).

Among the AO adducts of the active hydrogen-containing compound (a), polyether polyols having a hydroxyl value of 31 to 40 (mg KOH / g) and a content of terminal oxyethylene units of 14 to 17% by weight are polyethers Polyol having a hydroxyl value of 20 to 35 (mg KOH / g), a content of terminal oxyethylene units of 8 to 12% by weight, and a total of oxyethylene units of 15 to 25% by weight as a polyol (A1) Polyether polyol (A3) having polyether polyol (A2) as an ether polyol, a hydroxyl value of 250 to 310 (mg KOH / g), and a content of terminal oxyethylene units of 5 to 15% by weight It has a hydroxyl value of 20 to 30 (mg KOH / g), and the content of terminal oxyethylene units is 12% by weight. The polyether polyol is a example less than 15% by weight and polyether polyol (A4).
In the present invention, the number average functional group number of (A1) is 2.5 to 3.5, and the number average functional group number of (A2) is 1.5 to 2.5, and in (A3) The number average functional group number is 2.5 to 3.5, and the number average functional group number of (A4) is 3.5 to 4.5.
In addition, about "number average functional group number", for example, when it contains multiple types of thing which satisfy | fills a hydroxyl value and content of a terminal oxyethylene unit as polyether polyol (A1) in a polyol component (A), The number average functional group number means the functional group number which carried out the number average of these functional group numbers.
Further, the functional group number of each polyether polyol in the polyol component (A) is considered to be the same as the number of active hydrogens of the active hydrogen-containing compound (a) which is the starting material.

In (A1), the active hydrogen-containing compound (a) is preferably a monohydric or dihydric or higher alcohol having 2 to 10 carbon atoms, more preferably 2 to 10 carbon atoms, from the viewpoint of resin strength. Alcohol, particularly preferably glycerin.
In (A2), the active hydrogen-containing compound (a) is preferably a monohydric or dihydric or higher alcohol having 2 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms from the viewpoint of formability. Alcohol, particularly preferably propylene glycol.
In (A3), the active hydrogen-containing compound (a) is preferably a monohydric or dihydric or higher alcohol having 2 to 10 carbon atoms, more preferably 2 to 10 carbon atoms, from the viewpoint of resin strength. Alcohol, particularly preferably glycerin.
In (A4), the active hydrogen-containing compound (a) is preferably a monohydric or dihydric or higher alcohol having 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms from the viewpoint of resin strength. Alcohol, particularly preferably pentaerythritol.

The number average functional group number of (A1) is preferably 3 from the viewpoint of resin strength.
The number average functional group number of (A2) is preferably 2 from the viewpoint of formability.
The number average functional group number of (A3) is preferably 3 from the viewpoint of resin strength.
The number average functional group number of (A4) is preferably 4 from the viewpoint of resin strength.

The hydroxyl value of (A1) is preferably 33 to 38 (mg KOH / g), particularly preferably 34 to 37 (mg KOH / g), from the viewpoint of resin strength.
The hydroxyl value of (A2) is preferably 26 to 31 (mg KOH / g), particularly preferably 27 to 30 (mg KOH / g), from the viewpoint of resin strength.
The hydroxyl value of (A3) is preferably 265 to 300 (mg KOH / g), particularly preferably 270 to 295 (mg KOH / g), from the viewpoint of resin strength.
The hydroxyl value of (A4) is preferably 25 to 30 (mg KOH / g), particularly preferably 26 to 30 (mg KOH / g), from the viewpoint of resin strength.
In the present invention, the hydroxyl value means "56100 / molecular weight per hydroxyl group" and is mg of KOH equivalent to neutralize 1 g of the sample. Here, 56100 indicates the number of mg of KOH 1 mole. The method for measuring the hydroxyl value may be a known method as long as it can measure the value of the above definition, and is not particularly limited. For example, the method described in JIS K1557-1 can be mentioned.

Specifically as a polyether polyol (A1), what added 14-20 mol of EO to what added 60-75 mol of PO to glycerol etc. are mentioned.
As polyetherpolyol (A2), specifically, 8 to 10 moles of EO are added to those obtained by adding 45 to 55 moles of PO to propylene glycol, and then 3 to 4 moles of PO are further added, followed by 8 more EO. What added -10 mol etc. is mentioned.
As polyether polyol (A3), what added 1-2 mol of EO to what added 7-9 mol of PO to glycerol specifically, etc. are mentioned.
Specific examples of the polyether polyol (A4) include those obtained by adding 20 to 30 mol of EO to those obtained by adding 105 to 130 mol of PO to pentaerythritol.

In the present invention, the polymer polyol (L) is obtained by polymerizing the vinyl monomer (b) in the presence of a radical polymerization initiator in the polyether polyol (A4) (A4) and polymer fine particles (A5). A vinyl monomer (b) is acrylonitrile and styrene, and the weight ratio of acrylonitrile to styrene (acrylonitrile / styrene) in (b) is 60/40 to 75/25, It is a polymer polyol whose content of (A5) in L) is 25 to 35% by weight based on the weight of (L).
Specific examples of the polymerization method include the methods described in U.S. Pat. No. 3,383,351, JP-B-39-25737, and the like.

As a radical polymerization initiator, those which form free radicals to initiate polymerization can be used, and 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), Azo compounds such as 2,2'-azobis (2-methylbutyronitrile); organic peroxides such as dibenzoyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide and persuccinic acid; persulfates And inorganic peroxides such as perborate; and the like. In addition, these can use 2 or more types together.

Vinyl monomers (b) are acrylonitrile and styrene.
The weight ratio of acrylonitrile to styrene (acrylonitrile / styrene) in the vinyl monomer (b) is 60/40 to 75/25.

The content of (A1) in (A) is 50 to 55% by weight based on the weight of (A).
The content of (A2) in (A) is 20 to 25% by weight based on the weight of (A).
The content of (A3) in (A) is 3 to 7% by weight based on the weight of (A).
The content of (L) in (A) is 15 to 25% by weight based on the weight of (A).
The content of polymer fine particles (A5) in (A) is 4 to 8% by weight based on the weight of (A).

The blowing agent (C) preferably contains water, more preferably only water.
The content of water is preferably 1 to 7% by weight, and more preferably 1 to 6% by weight, based on the total weight of the polyol component (A), from the viewpoint of expansion ratio and disintegrability of the foam.
When the water content is 1% by weight or more, the expansion ratio is sufficient, and the filling in the mold is sufficient at the time of foam molding. If it is 7% by weight or less, excessive foaming gas is not generated, and the foam is less likely to collapse.
As the blowing agent (C), it is preferable to use only water, but if necessary, hydrogen atom-containing halogenated hydrocarbon, low boiling point hydrocarbon and liquefied carbon dioxide gas may be used in combination.

As a hydrogen atom-containing halogenated hydrocarbon-based foaming agent, HCFC (hydrochlorofluorocarbon) (HCFC-123, HCFC-141b, HCFC-22 and HCFC-142b, etc.); HFC (hydrofluorocarbon) (HFC-134a, HFC- 152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mfc, etc.); and HFO (hydrofluoroolefin) (HFO-1336mzzZ, etc.).
Among them, preferred are HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mfc and mixtures of two or more of these.
The content of the hydrogen atom-containing halogenated hydrocarbon is preferably 50% by weight or less, more preferably 5 to 5% by weight, based on the total weight of the polyol component (A), from the viewpoints of expansion ratio and foam disintegration. It is 45% by weight.

The low boiling point hydrocarbon is a hydrocarbon having a boiling point of -5 to 70 ° C., and butane, pentane, cyclopentane, a mixture thereof and the like can be mentioned.
The content of low-boiling hydrocarbon is preferably 30% by weight or less, more preferably 25% by weight or less, based on the total weight of the polyol component (A), from the viewpoint of expansion ratio and foam disintegration. is there.
The content of the liquefied carbon dioxide gas is preferably 30% by weight or less, more preferably 25% by weight or less, based on the total weight of the polyol component (A), from the viewpoint of expansion ratio and disintegrability of the foam. .

The catalyst (D) contains the following (D1-1) and (D1-2).
Catalyst (D1-1): N- (3-aminopropyl) -N, N ′, N′-trimethyl-bis (2-aminoethyl) ether catalyst (D1-2): N, N′-bis [3- Dimethylaminopropyl] urea

  The total content of (D1-1) and (D1-2) in the polyol mixture (P) is 0.1 to 1% by weight from the viewpoint of demoldability based on the weight of the polyol component (A) is there. It is preferably 0.2 to 0.8% by weight, particularly preferably 0.3 to 0.8% by weight, and most preferably 0.5 to 0.6% by weight.

  The weight ratio {(D1-1) / (D1-2)} between (D1-1) and (D1-2) is preferably 0.1 / 99.9 to 99.9 / 0.1, and more preferably It is preferably 10/90 to 90/10, particularly preferably 30/70 to 70/30, and most preferably 40/60 to 50/50.

As the catalyst (D), in addition to the above (D1-1) and (D1-2), other catalysts (D2) [dimethylamine · methylamine · 1,6-hexanediol polymer, {tertiary amine (triethylamine) , Triethylenediamine, bis-2-dimethylaminoethyl ether / dipropylene glycol, N, N-dimethylaminopropylpropanolamine, N, N, N ', N'-tetramethylhexamethylenediamine etc.}, carboxylic acids of tertiary amines Acid salts, carboxylic acid metal salts (such as potassium acetate, potassium octylate and stannas octoate) and organic metal compounds {tin catalysts (such as dibutyltin dilaurate), titanium catalysts, bismuth metal catalysts, etc. may be used.
The total content of the other catalysts (D2) in the polyol mixture (P) is preferably 50% by weight or less, more preferably 20% by weight or less based on the weight of the catalyst (D) from the viewpoint of moldability is there.

The additive (E) contains triazole (E1).
The triazole (E1) exhibits the function of capturing an aldehyde, and specifically, 1,2,3-triazole, 1,2,4-triazole, 3-butyl-1,2,4-triazole And 4-amino-1,2,4-triazole and the like.
Among (E1), 1,2,4-triazole is preferable from the viewpoint of the effect of reducing aldehyde.

As an additive (E), you may contain another additive (E2) from a viewpoint of the aldehyde reduction effect other than a triazole (E1).
As another additive (E2), the thing of following (1)-(5) is mentioned.
(1) Ester of Polyhydric Alcohol and Polycarboxylic Acid or an Ester-Forming Derivative Thereof A dihydric alcohol (ethylene glycol, diethylene glycol, 1,2- or 1,3-propylene glycol, 1,3-alcohol) Or 1,4-butanediol, 1,6-hexanediol and neopentyl glycol, those obtained by condensing these with lactones (such as ε-caprolactone), etc., polyether polyols (preferably diols), and these with trivalent or more And mixtures thereof with polyhydric alcohols (eg, glycerin and trimethylolpropane). The polycarboxylic acid or its ester-forming derivative is an acid anhydride and lower alkyl (carbon number of alkyl group: 1 to 4) ester, etc., and is adipic acid, sebacic acid, maleic anhydride, phthalic anhydride and dimethyl terephthalate Etc.
(2) Condensation reaction product with carboxylic acid anhydride and AO (3) AO (EO, PO etc.) adduct of the above (1) and (2) (4) Polylactone polyol For example, polyalcohol as initiator What is obtained by ring-opening polymerization of lactones (ε-caprolactone etc.) may, for example, be mentioned.
(5) Polycarbonate polyol For example, the reaction product of the said polyhydric alcohol and alkylene carbonate, etc. are mentioned.

  The content of (E1) in the polyol mixture (P) is 0.01 to 10% by weight based on the weight of the polyol component (A), and from the viewpoint of moldability, 0.05 to 5% by weight is preferable. More preferably, it is 0.1 to 3% by weight, and most preferably 0.2 to 1% by weight.

The polyol mixture (P) contains, in addition to the above-mentioned polyol component (A), blowing agent (C), catalyst (D) and additive (E), a foam stabilizer (F), an auxiliary component (G), etc. You may
As a foam stabilizer (F), what is used for manufacture of a urethane foam can be used, and a silicone foam stabilizer etc. are mentioned.
As silicone foam stabilizers, polyether-modified dimethylsiloxane foam stabilizers ["SZ-1328", "SZ-1346" and "SF-2962" manufactured by Toray Dow Corning Co., Ltd., and Momentive Performance Materials "L-3640" and "L-540", etc. manufactured by TDK, "SRX-253" manufactured by Toray Dow Corning Co., Ltd., and a dimethylsiloxane-based foam stabilizer, and "TEGOSTAB B8738LF2" and "TEGOSTAB" manufactured by EVONIK. B8715 LF2 etc.] and the like.
The amount of the foam stabilizer (F) used is preferably 3% by weight or less, more preferably 2.5% by weight or less, from the viewpoint of moldability, based on the total weight of the polyol component (A).

In the present invention, if necessary, known auxiliary components (G) such as colorants, flame retardants, anti-aging agents and antioxidants may be further contained, and they may be reacted in the presence thereof. Colorants include dyes and pigments. The flame retardants include phosphoric acid esters and halogenated phosphoric acid esters. Anti-aging agents include triazole-based and benzophenone-based anti-aging agents and the like. The antioxidants include hindered phenol type and hindered amine type antioxidants and the like.
The amount of the auxiliary component (G) used is preferably 1% by weight or less based on the total weight of the polyol component (A), from the viewpoint of curability and mechanical properties of urethane foam, and the flame retardant is 5% by weight or less is preferable from the viewpoint of curability and mechanical properties of polyurethane foam, and more preferably 2% by weight or less, and 1% by weight or less from the viewpoint of curability and mechanical properties of urethane foam The amount is preferably 0.5% by weight or less, and the antioxidant is preferably 1% by weight or less, more preferably 0.01 to 0.5% by weight from the viewpoint of the curability and mechanical properties of the urethane foam. is there.

In the present invention, the urethane foam layer (3) comprises a polyol mixture (P) containing a polyol component (A), a foaming agent (C), a catalyst (D) and an additive (E), and a polyisocyanate component (B) And urethane foam made by reacting them.
As the polyisocyanate component (B), those conventionally used for polyurethane can be used. As such polyisocyanate, aromatic polyisocyanate (B1), linear or branched aliphatic polyisocyanate (B2), alicyclic polyisocyanate (B3), araliphatic polyisocyanate (B4), modified products thereof (B5) and a mixture of two or more of these.

  As the aromatic polyisocyanate (B1), aromatic diisocyanate having 6 to 16 carbon atoms (excluding carbon in NCO groups; the same applies to the following polyisocyanates), aromatic triisocyanate having 6 to 20 carbon atoms, and these Crude products of isocyanate and the like can be mentioned. As specific examples, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 4,4'-diphenylmethane diisocyanate ( MDI), polymethylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4' '-triisocyanate and the like.

  As a linear or branched aliphatic polyisocyanate (B2), a C6-C10 aliphatic diisocyanate etc. are mentioned. Specific examples thereof include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate.

  As alicyclic polyisocyanate (B3), a C6-C16 alicyclic diisocyanate etc. are mentioned. Specific examples include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate and norbornane diisocyanate.

  As an aromatic aliphatic polyisocyanate (B4), a C8-C12 aromatic aliphatic diisocyanate etc. are mentioned. Specific examples thereof include xylylene diisocyanate and α, α, α ′, α′-tetramethyl xylylene diisocyanate.

  The modified products (B5) include the modified products of the above (B1) to (B4) (urethane group, carbodiimide group, allophanate group, urea group, biuret group, isocyanurate group, oxazolidone group containing modified product etc.) Examples of modified polyisocyanates include carbodiimide-modified MDI and the like.

  The polyisocyanate component (B) is preferably a modified product of the aromatic polyisocyanates (B1) and (B1) from the viewpoint of demoldability, more preferably TDI, crude TDI, MDI, crude MDI and isocyanates thereof It is at least one selected from the group consisting of modified products, and particularly preferably at least one selected from the group consisting of MDI, crude MDI and modified products thereof.

  The isocyanate index [equivalent ratio of (NCO group / OH group) x 100] when reacting the polyol component (A) and the polyisocyanate component (B) is preferably 50 to 300, and more preferably from the viewpoint of demoldability. Preferably 70 to 200, particularly preferably 80 to 125, most preferably 95 to 115.

The density of the urethane foam layer (3) is 0.15 to 0.25 g / cm ³ , and from the viewpoint of formability, 0.155 to 0.245 g / cm ³ is preferable, and more preferably 0.16 to 0 it is a .24g / cm ^3.

 In the present invention, the isocyanate index (index) [equivalent ratio of (NCO group / OH group) x 100] of the mixture comprising the polyol mixture (P) and the polyisocyanate component (B) is the curability of the foam and the foam From the viewpoint of formability, 70 to 140 is preferable, more preferably 75 to 130, and particularly preferably 80 to 120.

  In the present invention, the time from mixing the polyol mixture (P) and the polyisocyanate component (B) to removing the urethane-integrated foam is 45 to 75 seconds, but from the viewpoint of demolding properties, 50 to 70 seconds are preferable.

An example of the manufacturing method of the urethane integral foam molding of this invention is shown below.
First, polyol component (A), blowing agent (C), catalyst (D), additive (E) and, if necessary, foam stabilizer (F) and auxiliary component (G) are mixed in predetermined amounts, and polyol mixture (P) Make
The polyol mixture (P) and the polyisocyanate component (B) are then rapidly mixed using a polyurethane foam (low or high pressure foam, preferably high pressure foam) or a stirrer. The resulting mixed solution is used in a closed injection type crash pad molding die (preferably at a molding die temperature of 25 to 50 ° C.) in which the resin surface material (1) and the base material (2) are set on one side. It is injected, foamed and cured, and after a predetermined time, it is demolded to obtain a urethane integrated foam molded article having uniform density distribution. The auxiliary component (G) and the like can also be used by mixing with the polyisocyanate component (B).
It is preferable that it is 100 to 400%, and, as for the filling rate [(density at the time of mold foaming / density at the time of free foaming) x 100] at the time of injection | pouring, it is more preferable that it is 150 to 350%.
In addition, the content of acetaldehyde measured from the molded urethane integrated foam is 67 μg / kg or less.

  The urethane integrated foam molded article of the present invention comprises a polyol mixture (P) and a polyisocyanate component (B), and a urethane foam layer (3) is formed between the resin skin material (1) and the base material (2). Since it can be integrally molded, it can be suitably used as an automotive instrumental panel.

  Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereby.

Examples 1 to 4 and Comparative Example 1
A premix containing a polyol component (A), a foaming agent (C), a catalyst (D) and an additive (E) shown in Table 1 using a high-pressure foaming machine (polymer engineering, manufactured by mini-RIM machine) And a polyisocyanate component (B), and the base material and the resin surface material are respectively set on the upper and lower sides of the closed mold for instrumental panel for automobile, and injection molding is performed on the resin surface material set in the lower mold. An integral foam (instrumental panel for automobile) was obtained. In addition, foaming conditions are as follows.

<Foaming conditions>
Molding machine: MINI-RIM L type head manufactured by Polymer Engineering Co., Ltd. Discharge pressure: 15 to 17 MPa
Discharge amount: 150 g / sec Liquid temperature: 25 to 35 ° C.
・ Type temperature: 30 to 40 ° C
Demolding time: 60 seconds (time to open the mold lid)

Polyol component (A)
(1) Polyether polyol (A1-1): product obtained by adding 17 mol of EO to product obtained by adding 66 mol of PO to glycerin (hydroxyl value = 36, content of terminal EO unit = 16% by weight)
(2) Polyether polyol (A1-2): product obtained by adding 73 mol of PO to glycerin and 16 mol of EO (hydroxyl value = 34, content of terminal EO unit = 14% by weight)
(3) Polyether polyol (A2-1): 9.1 moles of EO added to 50 moles of PO added to propylene glycol, then 3.5 moles of PO added and 9.1 moles of EO added (hydroxyl value = 28, EO units Content = 20 wt%, content of terminal EO unit = 10 wt%)
(4) Polyether polyol (A3-1): One obtained by adding 1.4 mol of EO to one obtained by adding 7.7 mol of PO of glycerin (hydroxyl value = 281, content of terminal EO unit = 10% by weight)
(5) Polymer polyol (L): Polymer polyol obtained by polymerizing vinyl monomer (b) in the presence of a radical polymerization initiator in polyether polyol (A4). (Polyether polyol (A4) added to 116 moles of PO of pentaerythritol added with 25 moles of EO (hydroxyl value = 28, terminal EO unit content = 14 wt%), vinyl monomer (b) acrylonitrile / styrene = Polymerized at 67/33% by weight, the content of polymer fine particles (A5) is 30% by weight based on the weight of (L))

Polyisocyanate component (B): Modified MDI isocyanate (NCO content = 30.4%, CEI-264 manufactured by Tosoh Corp.)

Blowing agent (C): water

Catalyst (D)
(D1-1): N- (3-aminopropyl) -N, N ', N'-trimethyl-bis (2-aminoethyl) ether (hydroxyl value = 276)
(D1-2): N, N′-bis [3-dimethylaminopropyl] urea (hydroxyl value = 730)
(D2-1): dimethylamine, methylamine, 1,6-hexanediol polymer (hydroxyl value = 230)
(D2-2): N, N-dimethylaminopropylpropanolamine (hydroxyl value = 522)
(D2-3): bis-2-dimethylaminoethyl ether / dipropylene glycol = 70/30% by weight
(D2-4): triethylamine

Additive (E)
(E1-1): 1,2,4-triazole (E2-1): adipic acid, ε-caprolactone, neopentyl glycol polycondensate (manufactured by Daicel, PCL-220AL)

<Physical property test>
(1) Density (g / cm ³ ) of urethane foam layer: Measured in accordance with JIS K6400.
(2) Acetaldehyde content of urethane integrated foam molded product (instrumental panel for automobile):
(I) Remove the mold from the mold and put the automotive instrumental panel within 2 weeks into a bag (1000 × 1700 mm, volume 300 L) and heat at 65 ° C. for 2 hours.
(Ii) Collect all the gas in the bag into a DNPH pipe (GL Science Inc., Inert Sep mini AERO DNPH) at a speed of 2 L / min or less using a pump.
(Iii) Using a syringe or the like, acetonitrile (5 mL / per DNPH tube) is connected to the DNPH tube for extraction, and measurement of acetaldehyde content is carried out using the following measuring instrument and conditions.
[Acetaldehyde measuring instrument and measurement conditions]
Measuring instrument: HPLC-VP manufactured by Shimadzu Corporation
・ Detector: UV 360 nm
・ Column: GL Science Inc. INERTSIL ODS-80
Eluent: HPLC acetonitrile / water = 55/45 volume ratio Column temperature: 40 ° C
The acetaldehyde content determined by the following formula is shown in Table 1.
Acetaldehyde content (μg / kg) = {total amount of acetaldehyde detected (μg)} / {weight of automotive instrumental panel (kg)}

  As apparent from the results of Table 1, the examples of the present invention can significantly reduce the acetaldehyde content of the automotive instrumental panel as compared with the comparative example.

  In the method for producing a urethane integrated foam molded article according to the present invention, in the case of molding by reacting the polyol mixture (P) and the polyisocyanate component (B) (start of mixing of raw materials including these), other materials (for example, resin It can be used as an instrumental panel for automobiles because it can be integrally molded with a skin material, another organic substance as a base material, etc. and an inorganic substance).

Claims (2)

The urethane foam layer (3) is integrally molded between the resin surface material (1) and the base material (2) by using a mold, and the urethane foam layer (3). Is a urethane foam formed by reacting a polyol mixture (P) containing a polyol component (A), a blowing agent (C), a catalyst (D) and an additive (E) with a polyisocyanate component (B), The polyol component (A) contains the following polyether polyols (A1) to (A3) and the following polymer polyol (L), and (L) contains the following polymer fine particles (A5) in the following polyether polyol (A4) The polymer polyol is contained, and the content of (A1) in (A) is 50 to 55% by weight based on the weight of (A), and the content of (A2) is based on the weight of (A) 20 to 25% by weight, (A3 Content of 3-7% by weight based on the weight of (A), content of (L) is 15-25% by weight based on the weight of (A), and the content of polymer microparticles (A5) Is 4 to 8% by weight based on the weight of (A), the catalyst (D) contains the following (D1-1) and (D1-2), and (D1-1) and (D) in (P) The total content of D1-2) is 0.1 to 1% by weight based on the weight of (A), the additive (E) contains the following (E1), and (P) in (P) The content of E1) is 0.01 to 10% by weight based on the weight of (A), and the urethane integrated foam is removed after mixing of the polyol mixture (P) and the polyisocyanate component (B) is started. Acetaldehyde is 45 to 75 seconds to mold and is measured from a molded urethane integral foam. Content is not more than 67μg / kg, the production method of the urethane foam layer (3) a urethane integrally foamed molded article density of 0.15~0.25g / cm ³ of.
(A1): polyether having a number average functional group number of 2.5 to 3.5, a hydroxyl value of 31 to 40 (mg KOH / g), and a content of terminal oxyethylene units of 14 to 17% by weight Polyol (A2): The number average functional group number is 1.5 to 2.5, the hydroxyl value is 20 to 35 (mg KOH / g), and the content of terminal oxyethylene units is 8 to 12% by weight, Polyether polyol (A3) in which the total of oxyethylene units is 15 to 25% by weight: the number average functional group number is 2.5 to 3.5, the hydroxyl value is 250 to 310 (mg KOH / g), and the terminal Polyether polyol (A4) having a content of oxyethylene units of 5 to 15% by weight: The number average functional group number is 3.5 to 4.5, and the hydroxyl value is 20 to 30 (mg KOH / g), Terminal oxye Polyether polyol (A5): polymer fine particle polymer of vinyl monomer (b) having a content of ren units of more than 12% by weight and less than 15% by weight Polymer polyol (L): radical polymerization in polyether polyol (A4) A polymer polyol containing (A4) and polymer fine particles (A5) obtained by polymerizing a vinyl monomer (b) in the presence of an initiator, wherein the vinyl monomer (b) is acrylonitrile and styrene, (b Weight ratio of acrylonitrile to styrene (acrylonitrile / styrene) is 60/40 to 75/25, and the content of (A5) in (L) is 25 to 35 weight based on the weight of (L) % Polymer polyol catalyst (D1-1): N- (3-aminopropyl) -N, N ', N'-trimethyl-bis (2-aminoethyl) Ether catalyst (D1-2): N, N′-bis [3-dimethylaminopropyl] urea additive (E1): triazole The polyisocyanate component (B) according to claim 1, which contains at least one selected from the group consisting of 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate and modified products thereof. Of urethane integrated foam molded article.