JP2010031242A - Polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane resin having excellent combustibility (flame retardance) even when a flame retardant is not contained or a small amount thereof is contained. <P>SOLUTION: An un-foamed or a foamed polyurethane resin having a concentration of vinyl polymerizable functional groups of 0.05-6 mmol/g in the resin is used. The un-foamed or the foamed polyurethane resin is obtained by reacting an active hydrogen component (A) with an organic polyisocyanate (B). Furthermore, the un-foamed or the foamed polyurethane resin containing an active hydrogen compound (a) of a specific composition having an active hydrogen-containing group and a terminal vinyl polymerizable functional group of a specified composition; and one or more kinds of compounds (c), as necessary, having the vinyl polymerizable functional group and no active hydrogen-containing group, or containing (a) and/or (c); and one or more kinds of active hydrogen compounds (b) having no vinyl polymerizable functional group in (A) is preferably used. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyurethane resin. Specifically, it relates to the flame retardancy of non-foamed or foamed polyurethane resins.

Polyurethane resins are easy to process and have excellent properties such as heat resistance, weather resistance and mechanical properties, and are widely used in many industrial products and daily products such as electronic and electrical equipment.
Moreover, a flame retardant is provided and the polyurethane resin molded product is made flame retardant. (For example, see Non-Patent Document 1)

Polyurethane resin handbook (published by Keiji Iwata, published by Nikkan Kogyo Shimbun) Issued on September 25, 1987 P167,174-177

  However, application of a large amount of flame retardant may cause deterioration of resin physical properties such as reduction of resin strength. An object of the present invention is to provide a polyurethane resin excellent in combustibility (flame retardancy) even if it does not contain a flame retardant or has a small content.

  The present invention is a non-foamed or foamed polyurethane resin characterized in that the concentration of vinyl polymerizable functional groups in the resin is 0.05 to 6 mmol / g.

  The polyurethane resin of the present invention is superior in flammability (flame retardancy) as compared with conventional polyurethane resins. Moreover, it is excellent also in resin strength, such as compression hardness.

  In the present invention, the concentration of the vinyl polymerizable functional group in the polyurethane resin is 0.05 to 6 mmol / g, preferably 0.08 to 4 mmol / g, more preferably 0.1 to 3.5 mmol / g, particularly preferably. Is 0.2 to 3 mmol / g. When the concentration of the vinyl polymerizable functional group in the resin is less than 0.05 mmol / g, the resulting resin has insufficient flammability (flame retardancy). When the concentration of the vinyl polymerizable functional group exceeds 6 mmol / g, brittleness occurs.

Here, the density | concentration of the vinyl polymerizable functional group in resin was computed using the peak intensity | strength (peak area) measured by the Fourier-transform infrared absorption analysis method (FT-IR). In FT-IR, the peak of the vinyl polymer group is detected at 896 to 935 cm ⁻¹ . The peak area of the vinyl polymer group of the polyurethane resin of the sample is K, and the peak of the vinyl polymer group of the polyurethane resin obtained by adding an excessive amount of a polymerization inhibitor to the raw material having the same composition as the raw material of the sample polyurethane resin. When L is L, the vinyl polymer group concentration in the resin is obtained by the following equation.
Vinyl polymer group concentration in resin = M × (K / K ′) / (L / L ′)

  Here, M represents the molar concentration (calculated value) of the vinyl polymer group in the raw material relative to the total weight of the raw material of the polyurethane resin. K ′ is the peak area of the structure not involved in the reaction in the sample polyurethane resin, and L ′ is the polyurethane obtained by adding an excess amount of a polymerization inhibitor to the raw material having the same composition as the raw material of the sample polyurethane resin. The peak area of the same structure as K ′ that does not participate in the reaction in the resin is shown. For example, the structure of K ′ and L ′ represents an aromatic ring.

In the present invention, any method may be used as a method for setting the concentration of the vinyl polymerizable functional group in the resin to 0.05 mmol / g or more, and is not particularly limited. It is obtained by reacting the component (A) with the organic polyisocyanate (B). In (A), it has an active hydrogen-containing group and a vinyl polymerizable functional group represented by the following general formula (1). one or more active hydrogen compounds (a) selected from a1) to (a3) and, if necessary, one or more compounds (c) having a vinyl polymerizable functional group and no active hydrogen-containing groups. Or a resin containing (a) and / or (c) and one or more active hydrogen compounds (b) having no vinyl polymerizable functional group, and the unreacted vinyl polymerizable functional group is 0 .05mmol / How to leave or more.
(A1) Unsaturated carboxylic acid partial ester or partially unsaturated alkyl ether of polyol (a2) Unsaturated carboxylic acid partially amidated or partially unsaturated alkylated product of amine (a3) Unsaturated carboxylic acid partially thioester or partially unsaturated polyamine Alkyl thioether

［式中Ｒは、水素、炭素数１〜１５のアルキル基、または炭素数６〜２１のアリール基を表す。］

[Wherein R represents hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms. ]

  As a method for adjusting the amount of the unreacted vinyl polymerizable functional group, for example, by changing the concentration of the radical polymerization initiator used for producing the polyurethane resin, the unreacted vinyl polymerizable functional group in the resin is changed. A method for controlling the concentration can be mentioned. Specifically, when dicumyl peroxide (“PARK Mill D” manufactured by Nippon Oil & Fats Co., Ltd.) is used, it has a vinyl polymerizable functional group-containing active hydrogen compound (a) and a vinyl polymerizable functional group, and is active. Preferably it is 1.0 mol% or less with respect to the vinyl polymerizable functional group in the compound (c) which does not have a hydrogen containing group, More preferably, it is 0.5 mol% or less, Most preferably, it is 0.3 mol% or less.

  In addition, a method for increasing the concentration of vinyl polymerizable functional groups in the resin by lowering the temperature during the reaction to increase unreacted vinyl polymerizable functional groups, vinyl polymerizable functional group-containing active hydrogen compound (a) and vinyl A method of increasing the concentration of the vinyl polymerizable functional group in the resin by increasing the concentration of the vinyl polymerizable functional group in the compound (c) having a polymerizable functional group and not having an active hydrogen-containing group, an active hydrogen component ( Even if the method of increasing the concentration of unreacted vinyl polymerizable functional groups by significantly increasing the active hydrogen value of A) and greatly promoting the urethanization reaction, reducing the collision frequency between vinyl polymerizable functional groups, etc. Good.

Examples of the vinyl polymerizable functional group of the active hydrogen compound (a) having a vinyl polymerizable functional group used as necessary in the active hydrogen component (A) include a (meth) acryloyl group, an allyl group, a propenyl group, and 1-butenyl. 1 or more types chosen from group etc. are mentioned. Among these, (meth) acryloyl group, allyl group and propenyl group are preferable, and (meth) acryloyl group and allyl group are more preferable. Here, the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group, and the same description is used hereinafter.
Moreover, as an active hydrogen containing group of (a), 1 or more types chosen from a hydroxyl group, a mercapto group, a primary amino group, and a secondary amino group are mentioned, for example. Preferred are a hydroxyl group and a mercapto group, and more preferred is a hydroxyl group.

The active hydrogen compound (a) having a vinyl polymerizable functional group is a compound selected from the following (a1) to (a3), and two or more kinds may be used in combination.
(A1) Polyol [derived from polyhydric alcohol, polyhydric phenol, polyhydric alcohol or polyhydric phenol alkylene oxide (hereinafter abbreviated as AO) adduct, amine AO adduct, polyhydric alcohol and polycarboxylic acid or lactone Unsaturated polyester carboxylic acid ester or partially unsaturated alkyl ether [particularly (meth) acrylic acid ester or partial allyl ether]
(A2) Unsaturated carboxylic acid partially amidated product or partially unsaturated alkylated product of amine (particularly partially (meth) acrylamide or partially allylated product)
(A3) Unsaturated carboxylic acid partial thioester or partially unsaturated alkylthioether of polythiol [particularly partially (meth) acrylthioester or partially allylated product]

  Examples of the polyhydric alcohol used in the production of (a1) include dihydric alcohols having 2 to 18 carbon atoms (preferably 2 to 12) [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4- and 1 , 3-butanediol, 1,6-hexanediol, neopentyl glycol, etc.], C3-C18 (preferably 3-12) C3-C5 polyhydric alcohol [alkane polyol and its intramolecular or intermolecular] Dehydrates, such as glycerin, trimethylolpropane, pentaerythritol, sorbitan, diglycerine; sugars and derivatives thereof, such as α-methylglucoside, xylitol, glucose, fructose; etc.], and C 5-18 (preferably 5 ~ 12) 6 to 10 or more Polyhydric alcohols [6 to 10 valent alkane polyols, and intramolecular or intermolecular dehydrates of 6 to 10 valent alkane polyols or 3 to 5 valent alkane polyols such as dipentaerythritol; saccharides and derivatives thereof such as Sorbitol, mannyl, sucrose; etc.] and combinations of two or more thereof.

  Examples of the polyhydric phenol used in the production of (a1) include polyhydric phenols (monocyclic polyhydric phenols (hydroquinone, etc.), bisphenols (bisphenol A, bisphenol F, etc.)), trivalent to pentavalent polyhydric phenols (mono Ring polyhydric phenols (pyrogallol, phloroglucin, etc.), 3-5 valent, polyhydric phenolic formalin low condensates (number average molecular weight 1000 or less) (novolak resin, resol intermediate), etc.], 6-10 valent or More polyhydric phenols [hexavalent or higher polyhydric phenol compound formalin low condensate (number average molecular weight 1000 or less) (novolak resin, resol intermediate), etc.], polyhydric phenol and alkanolamine condensate (Mannich polyol) and combinations of two or more of these may be mentioned.

  Among the polyols used in the production of (a1), as the amine in the AO adduct of amine, for example, ammonia; alkanolamine having 2 to 20 carbon atoms [mono-, di- or triethanolamine, isopropanolamine, aminoethylethanol An amine etc.]; an alkylamine having 1 to 20 carbon atoms [methylamine, ethylamine, n-butylamine, octylamine etc.]; an alkylenediamine having 2 to 6 carbon atoms [ethylenediamine, hexamethylenediamine etc.]; 2-6 polyalkylene polyamine (degree of polymerization 2-8) [diethylenetriamine, triethylenetetramine, etc.]; C6-C20 aromatic amine [aniline, phenylenediamine, tolylenediamine, xylylenediamine, methylenedianiline, Diphenyl -Terdiamine, naphthalenediamine, anthracenediamine, etc.]; alicyclic amine having 4 to 15 carbon atoms [isophoronediamine, cyclohexylenediamine, etc.]; heterocyclic amine having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1 , 4-diaminoethylpiperazine and the like] and combinations of two or more thereof.

  Examples of AO to be added to polyhydric alcohol, polyhydric phenol, or amine include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4. -Or 2,3-butylene oxide, α-olefin oxide (5 to 30 or more carbon atoms), styrene oxide or the like and combinations of two or more thereof (when used in combination, random addition, block addition, these Any of the combinations may be used. Among these AOs, those having 2 to 8 carbon atoms are preferred, and those containing PO and / or EO as the main component and, if necessary, other AOs of 20% or less are more preferred. The addition reaction can be performed by a conventionally known ordinary method. The number of moles of AO added per molecule is preferably 1 to 70, more preferably 1 to 50. In the above and the following,% means mass% unless otherwise specified.

Among the polyols used in the production of (a1), examples of the polyhydric alcohol used for the polyester polyol include those described above. Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms [succinic acid. , Adipic acid, sebacic acid, maleic acid, fumaric acid, etc.], aromatic polycarboxylic acids having 8 to 18 carbon atoms [phthalic acid or its isomers, trimellitic acid, etc.], ester-forming derivatives of these polycarboxylic acids Examples include [an acid anhydride, a lower alkyl ester having 1 to 4 carbon atoms in an alkyl group, and the like] and a combination of two or more thereof. Examples of the lactone include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and combinations of two or more of these.
The polyol used in the production of (a) preferably has 3 to 10 hydroxyl groups, more preferably 3 to 6 hydroxyl groups.

Taking (a1) as an example of a partial (meth) acrylic acid ester and a partial allyl ether, for example, the polyol exemplified above is such that at least one hydroxyl group remains unreacted in one molecule. It is obtained by partial (meth) acryloylation or partial allylation with a halogenated (meth) acrylic or allyl halide at an equivalent ratio. As the halogenated (meth) acrylic, (meth) acryloyl chloride, (meth) acryloyl bromide, (meth) acryloyl iodide, and allyl halide include allyl chloride, allyl bromide, allyl iodide and these two types The above combination is mentioned. Alternatively, the above-described polyol and (meth) acrylic acid may be used for the esterification reaction by an ordinary method at an equivalent ratio such that at least one hydroxyl group remains unreacted in one molecule.
(A1) can also be obtained by adding the above AO to unsaturated carboxylic acids and derivatives thereof such as 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, or unsaturated alcohols such as allyl alcohol. Can do. In this case, among the AOs, those containing PO and / or EO as the main component and, if necessary, other AOs of 20% or less are preferable. The addition reaction can be performed by a conventionally known ordinary method. The added mole number of AO is preferably 1 to 70, more preferably 1 to 50.

  (A2) is a polyamine or alkanolamine among the above amines and the above-mentioned halogenated (meth) acrylic or allyl halide, and at least one amino group or hydroxyl group (in the case of alkanolamine) in one molecule. It is obtained by reacting at an equivalent ratio that remains unreacted.

The polythiol used for the production of (a3) preferably has 2 to 4 thiol groups and has 2 to 18 carbon atoms, such as ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-propanedithiol, 1,4-benzenedithiol, 1,2-benzenedithiol, bis (4-mercaptophenyl) sulfide, 4-t-butyl-1,2-benzenedithiol, ethylene glycol dithioglycolate, tri Examples include methylolpropane tris (thioglycolate) thiocyanuric acid, di (2-mercaptoethyl) sulfide, di (2-mercaptoethyl) ether, and combinations of two or more thereof.
(A3) can be obtained by reacting these polythiols with the above-mentioned halogenated (meth) acrylic or allyl halide at an equivalent ratio such that at least one thiol group remains unreacted in one molecule. .

The active hydrogen compound (a) has one or more vinyl polymerizable functional groups in the molecule. The number of vinyl polymerizable functional groups is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 7, particularly preferably 1 to 5, and most preferably 2 to 4. When the number of vinyl polymerizable functional groups is 1 or less, the effect of expressing the compression hardness is low, and when it exceeds 20, the effect gradually decreases.
(A) has one or more active hydrogen-containing groups, preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1 to 2. When the number of active hydrogen-containing groups is 1 to 8, the curability during molding of the polyurethane resin is good.
The number of vinyl polymerizable functional groups and the number of active hydrogen-containing groups in (a) are average numbers when (a) is not a single composition such as a reaction mixture.

The active hydrogen value of the active hydrogen compound (a) is preferably 10 to 1800, more preferably 20 to 1500, particularly preferably 30 to 1000, and most preferably 50 to 500.
Here, the active hydrogen value means “56100 / molecular weight per active hydrogen”, and corresponds to the hydroxyl value when the group having active hydrogen is a hydroxyl group. The hydroxyl value is mg of KOH corresponding to neutralizing 1 g of a sample and means “56100 / molecular weight per hydroxyl group”. Here, 56100 represents the mg number of 1 mol of KOH. The method for measuring the active hydrogen value may be a known method as long as it can measure the value defined above, and is not particularly limited. In the case of the hydroxyl value, for example, the method described in JIS K1557 can be mentioned.

  Among these (a), preferably (a1) and (a2), more preferably (a1), particularly preferably a partial allyl ether of a polyhydric alcohol or an AO adduct thereof, and a polyhydric alcohol. Alternatively, it is a partial (meth) acrylic ester of an AO adduct thereof, and most preferably a partial (meth) acrylic ester of a polyhydric alcohol or an AO adduct thereof.

If necessary, one or more compounds (c) having a vinyl polymerizable functional group and no active hydrogen-containing group can be used in the active hydrogen component (A).
Since (c) does not have an active hydrogen-containing group, in order to form a polyurethane resin, in (A), it always has a vinyl polymerizable functional group-containing active hydrogen compound (a) and / or a vinyl polymerizable functional group. Need to be used together with the active hydrogen compound (b).
Examples of the vinyl polymerizable functional group (c) include the same vinyl polymerizable functional groups as those in the active hydrogen compound (a) having a vinyl polymerizable functional group, and preferred ones are also the same.
The number of vinyl polymerizable functional groups in (c) is preferably 1 to 20, more preferably 1 to 10.
(C) may be contained in the active hydrogen component (A) together with (a) by producing (a) under production conditions in which (c) occurs simultaneously with (a) as a by-product.
As (c), aromatic hydrocarbon monomers [styrene, α-methylstyrene, etc.], unsaturated nitriles ((meth) acrylonitrile, etc.) and the like can be used. Includes the following (c1) to (c3).

(C1) Polyol [polyhydric alcohol, polyhydric phenol, polyhydric alcohol or polyhydric phenol AO adduct, amine AO adduct, polyester polyol derived from polyhydric alcohol and polycarboxylic acid or lactone, etc.] Unsaturated carboxylic acid ester or unsaturated alkyl ether [especially (meth) acrylic acid ester or allyl ether]
(C2) Unsaturated carboxylic acid amidation or unsaturated alkylation product of amine (particularly (meth) acrylamide or allylation product)
(C3) Unsaturated carboxylic acid thioester or unsaturated alkyl thioether of polythiol [especially (meth) acryl thioester or allylated product]
(C1) to (c3) are reacted so that, for example, in the production of (a1) to (a3), the reaction molar ratio of the raw materials used is changed so that no unreacted active hydrogen-containing group remains. Is obtained.

  The active hydrogen compound (a) having a vinyl polymerizable functional group and the compound (c) having a vinyl polymerizable functional group and having no active hydrogen-containing group are (a) and (c) used in (A). ) Mass ratio [the sum of (a) and (c) is 100] is preferably (a) :( c) = 100: 0 to 10:90, more preferably (a) :( c) = 100: 0 to 30:70, particularly preferably (a) :( c) = 99: 1 to 40:60.

In the active hydrogen component (A), in addition to the active hydrogen compound (a) having a vinyl polymerizable functional group and one or more compounds (c) having a vinyl polymerizable functional group and no active hydrogen-containing group, If necessary, you may contain the active hydrogen compound (b) which does not have a vinyl polymerizable functional group.
In addition, when using only (c) as a compound which has a vinyl polymerizable functional group, it is necessary to use (b) together.
(B) is a polyol having substantially no vinyl polymerizable functional group, and includes an AO adduct (b1) of an aliphatic amine, an AO adduct (b2) of an aromatic amine, an AO of a polyhydric alcohol or polyhydric phenol. Examples of the adduct (b3), the polyester polyol (b4), the polymer polyol (b5), and those exemplified as the polyol used for the production of the (a1) include those other than the above (polyhydric alcohols and the like). May be used in combination.
Here, “substantially has no vinyl polymerizable functional group” means that the total degree of unsaturation measured by the method described in JIS K-1557 is 0.2 meq / g or less.

Examples of the aliphatic amine (b1) include primary and / or secondary amines. The number of primary and / or secondary amino groups is preferably 1 to 4, more preferably 1 to 3. Yes, the number of active hydrogens derived from amino groups is preferably 2-8, more preferably 2-4.
Specifically, as (b1), the alkanolamine, the alkylamine having 1 to 20 carbon atoms, the alkylenediamine having 2 to 6 carbon atoms, and the alkylene group having 2 to 6 carbon atoms described in the section (a1) above are used. Polyalkylene polyamine (degree of polymerization 2 to 8) and the like. Preferred are alkanolamines and alkylenediamines.
Preferable AO to be added is one containing PO and / or EO as a main component and optionally containing other AO of 20% or less, and particularly preferably PO and a combination of PO and EO.
The AO addition reaction can be carried out by a conventionally known ordinary method, and as a catalyst used at the time of addition, a catalyst described in JP-A-2000-344881 as well as a commonly used alkali catalyst (KOH, CsOH, etc.) [ Tris (pentafluorophenyl) borane and the like], and catalysts (magnesium perchlorate and the like) described in JP-A-2002-308811 may be used (the same applies to the following AO adducts).

Examples of the aromatic amine (b2) include aromatic amines having 6 to 20 carbon atoms described in the section (a1). Preferred are aniline, phenylenediamine and tolylenediamine.
Preferable AO to be added is one containing PO and / or EO as a main component and optionally containing other AO of 20% or less, and particularly preferably PO and a combination of PO and EO.

Examples of the polyhydric alcohol (b3) include those exemplified as the polyhydric alcohol used in the production of (a1).
Examples of the polyhydric phenol (b3) include those exemplified as the polyhydric phenol used in the production of (a1).
Preferable AO to be added is one containing PO and / or EO as a main component and optionally containing other AO of 20% or less, and particularly preferably PO and a combination of PO and EO.

  Examples of the polyester polyol of (b4) include those exemplified as the polyester polyol used in the production of (a1) and the polycondensate of the polyhydric alcohol or polyphenol AO adduct (b3) and the polycarboxylic acid. Can be mentioned.

As the polymer polyol of (b5), those usually used for polyurethane resins, for example, the polyether polyol obtained by adding the AO to the polycarboxylic acid, the polyester polyol and its AO adduct, a low molecular weight polyol (for example, Obtained by polymerizing a vinyl monomer (acrylonitrile, styrene, etc.) in one or more polyols selected from the polyhydric alcohol), the alkanolamine, and an AO adduct (b3) of the polyhydric alcohol or polyhydric phenol. And polymer polyols, as well as mixtures thereof. Preferable AO is PO and / or EO. Among these, the polymer polyol obtained from (b3) is preferable.
The manufacturing method of (b5) can be performed similarly to the polymerization method in the conventional polymer polyol. For example, a method of polymerizing a vinyl monomer in the presence of a polymerization initiator in a polyol containing a dispersant as required (US Pat. No. 3,383,351, Japanese Examined Patent Publication No. 39-24737, Japanese Examined Patent Publication No. 47-47999 or And the method described in JP-A-50-15894. The polymerization can be carried out either batchwise or continuously, and can be carried out under normal pressure, increased pressure or reduced pressure. A solvent and a chain transfer agent can be used as necessary. The volume average particle diameter of the polymer in (b5) is preferably 0.5 to 15 μm.

(B) preferably has 2 to 8 hydroxyl groups, more preferably 2 to 6 hydroxyl groups, and the hydroxyl value of (b) is preferably 30 to 1900, more preferably 50 to 1600, particularly Preferably it is 80-1000.
Among these (b), (b1), (b2), and (b3) are preferable, (b2) and (b3) are more preferable, and (b2) and (b3) are particularly preferable. It is an AO adduct of polyhydric alcohol.

In addition, in the active hydrogen component (A), the active hydrogen compound (a) having a vinyl polymerizable functional group and / or one or more compounds having a vinyl polymerizable functional group and no active hydrogen-containing group ( By using c), a polyurethane resin excellent in flammability (flame retardant) can be obtained. However, in particular, when used for applications in which flammability is important, it has an aromatic ring as (b). Compound, ie, AO adduct (b2) of aromatic amine (b3), AO adduct (b31) of polyhydric phenol among (b3), Polyester polyol having an aromatic ring among (b4) (C8 as a structural unit) A polymer polyol (b51) having an aromatic ring among (b41) and (b5). [Preferably 10 to 80 percent of (b)] is preferably used.
Among (b) having these aromatic rings, (b2) and (b41) are preferable, and more preferably (B2) is an AO adduct of phenylenediamine and an AO adduct of tolylenediamine. In (b41), phthalic acid or its isomer and / or diester thereof and 1,4-butanediol, 1,2-butanediol, glycerin, and one or more selected from (b3) Polycondensates, particularly preferably phenylenediamine AO adducts and tolylenediamine AO adducts.

The concentration of the vinyl group-containing component in the active hydrogen component (A) (% by weight; in the following paragraph, “%” represents “% by weight”) is preferably 0.6 to 62%, more preferably 1 to 40%, and particularly preferably Preferably it is 2 to 20%. If it is 0.6% or more, the flexural strength of the polyurethane resin is easily developed, and if it is 62% or less, it is easy to advance the polymerization reaction simultaneously with the urethanization reaction.
Here, the concentration of the vinyl group-containing component was determined by adding a sufficient amount of an ethanol solution of potassium hydroxide to the active hydrogen component (Z gram) and subjecting it to alkali decomposition at 70 ° C. for 24 hours under hermetically sealed condition. The vinyl group-containing component (E gram) is fractionated and determined by the following formula.
Concentration of vinyl group-containing component (%) = (E / Z) × 100

The total of active hydrogen compound (a) having a vinyl polymerizable functional group and one or more compounds (c) having a vinyl polymerizable functional group and no active hydrogen-containing group in the active hydrogen component (A) The mass ratio of the active hydrogen compound (b) having no vinyl polymerizable functional group (the sum of (a), (b) and (c) is 100) is [(a) + (c)]: (b Is preferably 100: 0 to 0.5:
99.5, more preferably 75:25 to 1:99, particularly preferably 70:30 to 5:95
It is. When the total ratio of (a) and (c) is 0.5% or more, the compression hardness of the foam is easily developed, and when it is 75% or less, it is easy to proceed the polymerization reaction simultaneously with the urethanization reaction.

  As organic polyisocyanate (B) used by this invention, what is necessary is just a compound which has two or more isocyanate groups in a molecule | numerator, and what is normally used for manufacture of a polyurethane resin can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof.

The aromatic polyisocyanate includes 6 to 16 aromatic diisocyanates, 6 to 20 aromatic triisocyanates, and crude products of these isocyanates (excluding carbon in the NCO group; the following isocyanates are also the same). Is mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, Examples include 4′-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, and the like.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.
Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.

Specific examples of the modified polyisocyanate include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.
The organic polyisocyanate (B) is preferably an aromatic polyisocyanate, more preferably selected from 2,4′- and / or 4,4′-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and modified products thereof. One or more types of MDI-based polyisocyanates. The content of these main components in (B) is preferably 40% or more, more preferably 80% or more.

Isocyanate index (NCO INDEX) [(NCO group / active hydrogen atom-containing group) equivalent ratio x 100 when the active hydrogen component (A) and the organic polyisocyanate (B) are reacted to produce the polyurethane resin of the present invention ] Is preferably 50 to 250, more preferably 70 to 200, particularly preferably 75 to 180, and most preferably 80 to 160.

The polyurethane resin of the present invention may be a non-foamed polyurethane resin or a foamed polyurethane resin obtained by reacting (A) and (B) in the presence of the foaming agent (C). Among the foamed polyurethane resins, the effect of the present invention is great when applied to rigid polyurethane foam.
As the blowing agent (C) used as necessary in the present invention, water, a hydrogen atom-containing halogenated hydrocarbon, a low-boiling hydrocarbon, liquefied carbon dioxide gas, or the like is used, and two or more kinds may be used in combination.
Specific examples of the hydrogen atom-containing halogenated hydrocarbon include HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123 and HCFC-141b); HFC (hydrofluorocarbon) type (for example, HFC-245fa and HFC-). 365 mfc).
The low boiling point hydrocarbon is a hydrocarbon having a normal boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, and cyclopentane. Of these, pentane and cyclopentane are preferable, and cyclopentane is more preferable.
Among these (C), preferred are low-boiling hydrocarbons and low-boiling hydrocarbons and water in combination.

The amount of the foaming agent (C) used with respect to 100 parts of the active hydrogen component (A) is preferably 0.1 to 30 parts, more preferably 1 to 20 parts, with respect to water. The hydrogen atom-containing halogenated hydrocarbon is preferably 50 parts or less, more preferably 10 to 45 parts. The amount of the low-boiling hydrocarbon is preferably 0.1 to 50 parts, more preferably 1 to 40 parts, particularly preferably 10 to 30 parts, most preferably 15 to 25 parts per 100 parts of the active hydrogen component (A). It is. The amount of liquefied carbon dioxide is preferably 30 parts or less, more preferably 1 to 25 parts. When the low boiling point hydrocarbon and water are used in combination, the amount of water used is preferably 10 parts or less, more preferably 0.1 to 5 parts, particularly preferably 0.1 in addition to the above amount of low boiling point hydrocarbons. ~ 3 parts, most preferably 0.2-2 parts.
In the above and the following, “part” means “part by mass” unless otherwise specified.

When manufacturing the polyurethane resin of this invention, an additive (D) can be used as needed.
Among (D), examples of radical polymerization initiators include azo compounds (for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis). (1-acetoxy-1-phenylethane, etc.), organic peroxides (for example, dibenzoyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, etc.), a combination of peroxide and dimethylaniline And water-soluble radical polymerization initiators such as (redox catalyst).

Other additives (D) include foam stabilizers (dimethylsiloxane, polyether-modified dimethylsiloxane, etc.), urethanization catalysts (tertiary amine catalysts such as triethylenediamine, N-ethylmorpholine, diethylethanolamine, N , N, N ′, N′-tetramethylhexamethylenediamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, diaminobicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole, 1-isobutyl-2-methylimidazole, bis ( Dimethylaminoethyl) ether, 1,8-diazabicyclo- [5,4,0] -undecene-7, and / or metal catalysts such as stannous octylate, dibutylstannic dilaurate, lead octylate Etc.), flame retardant (phosphate ester, Rogenated phosphates, etc.), colorants (dyes, content, etc.), plasticizers (phthalates, adipates, etc.), organic fillers (synthetic short fibers, thermoplastic or thermosetting resins) Etc.), antioxidants (hindered phenols, hindered amines, etc.), anti-aging agents (triazoles, benzophenones, etc.), mold release agents (wax, metal soaps, or mixtures thereof) The reaction can be carried out in the presence of an additive. Moreover, you may use the additive [For example, (a) solution of an amine catalyst] which used the said (a) as a diluent.

The amount of each of the active hydrogen components (A) added to 100 parts of the foam stabilizer is preferably 10 parts or less, more preferably 0.01 to 7 parts, particularly preferably 0.05 to 5 parts, and most preferably 0. 1 to 3 parts. The urethanization catalyst is preferably 15 parts or less, more preferably 0.01 to 10 parts, particularly preferably 0.02 to 5.0 parts, and most preferably 0.1 to 3.5 parts. When the amount of the urethanization catalyst is 10 parts or less, it is easy to cause the polymerization reaction to proceed simultaneously with the urethanization reaction, and when it is 0.01 parts or more, a polyurethane resin having good curing properties can be obtained.
The flame retardant is preferably 50 parts or less, more preferably 1 to 40 parts, particularly preferably 3 to 30 parts, and most preferably 5 to 25 parts. The colorant is preferably 2 parts or less, more preferably 1 part or less. The plasticizer is preferably 50 parts or less, more preferably 20 parts or less, and particularly preferably 10 parts or less. The organic filler is preferably 50 parts or less, more preferably 40 parts or less, and particularly preferably 30 parts or less. The antioxidant is preferably 1 part or less, more preferably 0.01 to 0.5 part. The anti-aging agent is preferably 1 part or less, more preferably 0.01 to 0.5 part. The release agent is preferably 10 parts or less, more preferably 5 parts or less, and particularly preferably 3 parts or less.

An example of the method for producing the polyurethane resin of the present invention is as follows.
First, a predetermined amount of the active hydrogen component (A) and, if necessary, the foaming agent (C) and / or the additive (D) are mixed. Next, using a polyurethane foaming machine or a stirrer, a mixture obtained by rapidly mixing the mixture and the organic polyisocyanate (B) is poured into a mold, cured for a predetermined time, and then demolded to obtain a polyurethane resin. The mold may be either an open mold or a closed mold, and may be at room temperature or under heating (for example, 30 to 80 ° C.). The urethanization reaction is preferably a one-shot method in the prepolymer method because the viscosity of the stock solution in which each component is mixed increases.
The polyurethane resin of the present invention may be a slab foam, a molded product by RIM (reaction injection molding) method, and a foamed polyurethane resin by mechanical floss method.

  The polyurethane resin of the present invention can be obtained by reacting the polyurethane-forming reaction of (a) and / or (b) and (B) together with the polymerization of the vinyl polymerizable functional group of (a) and / or (c). The vinyl polymer chain part formed by the polymerization of vinyl polymerizable functional groups obtained by allowing the vinyl polymer chain part and the polyurethane chain part to crosslink is crosslinked to the polyurethane chain part formed by the polyurethane formation reaction. It is resin which has the structure made. Here, the polymerization of the vinyl polymerizable functional group and the polyurethane forming reaction under the conditions in which the vinyl polymer chain portion and the polyurethane chain portion are cross-linked cause the polymerization of the vinyl polymerizable functional group and the polyurethane forming reaction, It means that it is performed in parallel for at least a part of the period. In order to increase the cross-linking density and improve the mechanical properties, before the resin is formed by curing in one reaction, the other reaction is started and two reactions are performed simultaneously. desirable.

In the case of foamed polyurethane resin, the core density in mold foaming is preferably 80 kg / m ³ or less, more preferably 10 to 60 kg / m ³ , particularly preferably 10 to 50 kg / m ³ , and most preferably 10 ˜45 kg / m ³ . In free foam, the core density is preferably 50 kg / ^{m 3} or less, more preferably 10~40kg / ^{m 3,} particularly preferably 10~35kg / ^{m 3,} most preferably from 10 to 30 kg / ^{m 3.}

The aromatic ring concentration of the polyurethane resin of the present invention is preferably from 1.0 to 10 mmol / g, more preferably from 2.0 to 10.0 mmol / g, and even more preferably from 3.0 to 10 because flame retardancy is good. The amount is 8.0 mmol / g, particularly preferably 3.2 to 6.0 mmol / g, and most preferably 3.5 to 5.0 mmol / g.
The aromatic ring concentration in the polyurethane resin is represented by the number of moles of the aromatic ring in the total mass of raw materials used to obtain the polyurethane resin, and is represented by the following formula.
[(Total number of aromatic rings in raw material used to obtain polyurethane resin) / (total mass of raw material used to obtain polyurethane resin)] × 1000

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by this.

<Measurement method of vinyl polymerizable functional group concentration in resin>
The concentration of the vinyl polymerizable functional group (hereinafter also referred to as vinyl polymerizable group) in the resin was measured by the Fourier transform infrared absorption analysis method (FT-IR, manufactured by Varian, 660-IR was used). (Peak area) was used for calculation. In FT-IR, the peak of the vinyl polymer group is detected at 896 to 935 cm ⁻¹ . It was obtained by adding 1% by weight of hydroquinone, which is a polymerization inhibitor, to a raw material having the same composition as the raw material of the polyurethane resin of the sample, with respect to the total weight of the resin raw material. When the peak area of the vinyl polymer group of the polyurethane resin is L, the vinyl polymer group concentration in the resin is obtained by the following formula.
Vinyl polymer group concentration in resin = M × (K / K ′) / (L / L ′)
Here, M represents the molar concentration (calculated value) of the vinyl polymer group in the raw material relative to the total weight of the raw material of the polyurethane resin. K ′ is an aromatic peak area (710 to 790 cm ⁻¹ ) which is a structure not involved in the reaction in the sample polyurethane resin, and L ′ is an excess amount of a polymerization inhibitor in the raw material having the same composition as the raw material of the sample polyurethane resin. An aromatic peak area (710 to 790 cm ⁻¹ ) that does not participate in the reaction in the polyurethane resin obtained by addition and reaction is shown.

<Calculation method of aromatic ring concentration in urethane resin>
It calculated | required by the said formula.

The raw materials of the polyurethane foam resin in the following Examples 1 to 20 and Comparative Examples 1 to 6 are as follows.
(1) Active hydrogen compound containing vinyl polymerizable functional group (a)
(A1) A vinyl polymerizable functional group-containing active hydrogen compound having a hydroxyl value of 748 and a vinyl polymerizable functional group in the molecule of 4.4 mmol / g obtained by reacting sucrose and acrylic acid (a2) sucrose and methacrylic acid A hydroxyl group value of 953 and a vinyl polymerizable functional group-containing active hydrogen compound having a vinyl polymerizable functional group in the molecule of 2.4 mmol / g. (A3) A hydroxyl group value of sorbitol and acrylic acid reacted. 282, a vinyl polymerizable functional group-containing active hydrogen compound having a vinyl polymerizable functional group in the molecule of 2.4 mmol / g. (A4) A hydroxyl value of 86 obtained by reacting pentaerythritol with acrylic acid. Active hydrogen compound containing vinyl polymerizable functional group having a polymerizable functional group of 10.8 mmol / g

(2) Compound (c) having a vinyl polymerizable functional group and no active hydrogen-containing group
(C1) Pentaerythritol and acrylic acid are reacted, the hydroxyl value is 0, the vinyl polymerizable functional group in the molecule is 11.4 mmol / g, and there is no active hydrogen-containing group Compound (3) Active hydrogen compound having no vinyl polymerizable functional group (b)
(B1) A polyether polyol having a hydroxyl value of 499 obtained by block addition of 2.2 mol of EO and 3.9 mol of PO to toluenediamine (b2) A polyether polyol having a hydroxyl value of 673 obtained by adding 2.7 mol of PO to glycerin (b3) Polyether polyol having a hydroxyl value of 748 obtained by blocking addition of 2.7 mol of EO and 2.1 mol of PO to ethylenediamine (b4) Polyether polyol having a hydroxyl value of 449 obtained by blocking addition of 4.8 mol of EO and 4.0 mol of PO to ethylenediamine ( b5) Polyether polyol having a hydroxyl value of 395 obtained by adding 7.7 mol of PO to toluenediamine (b6) Polyether polyol having a hydroxyl value of 748 obtained by adding 4.1 mol of PO to ethylenediamine (b7) 3.0 mol of EO in toluenediamine And PO5.2 mol Polyether polyol having a hydroxyl value of 405 obtained by block addition

(4) Foaming agent (C)
(C1) Water (C2) Cyclopentane (C3) HCFC-141b
(C4) HFC-245fa
(C5) HFC-365mfc

(5) Additive (D)
(D1) Trichloropropyl phosphate (manufactured by Eighth Chemical Co., Ltd.)
(D2) Amine catalyst A (MS-181 manufactured by San Apro Co., Ltd.)
(D3) Amine catalyst B (manufactured by San Apro Co., Ltd. MS-177)
(D4) Catalyst C (DABCO K-15 manufactured by San Apro Co., Ltd.)
(D5) Polyethersiloxane polymer (“SH-193” manufactured by Toray Dow Corning Co., Ltd.)
(D6) Radical polymerization initiator: Dicumyl peroxide (“Park Mill D” manufactured by NOF Corporation)
(6) Organic polyisocyanate (B)
(B1) Crude MDI (“MR-200” manufactured by Nippon Polyurethane Industry Co., Ltd.), NCO% = 31.0

[Examples 1 to 20, Comparative Examples 1 to 6]
The manufacturing method of the polyurethane foam resin of Examples 1-20 and Comparative Examples 1-6 is as follows.
First, a predetermined amount of the active hydrogen component (A), the foaming agent (C), and the additives (D) such as a foam stabilizer and a urethanization catalyst, whose temperature was adjusted to 25 ± 5 ° C., were mixed. Organic polyisocyanate (B) adjusted to 25 ± 5 ° C. is added to this mixture so as to have a predetermined NCO INDEX, and is rapidly mixed at 4000 rpm × 6 seconds with a stirrer [Homodisper: made by Special Machine Co., Ltd.] Then, the mixed solution was immediately poured into an aluminum box without a canopy of 240 × 240 × 240 mm at 25 ° C. and subjected to free foaming to obtain a polyurethane foam resin.

Table 1 shows the measurement results of the core density, compression hardness, vinyl polymer group concentration in the resin, and flammability (combustion distance, time until combustion penetration) of the polyurethane foam resins obtained in the examples and comparative examples. It shows in Table 2.
<Measurement method of core density>
After molding by the above-mentioned method, a sample piece of 50 (length) x 50 (width) x 50 (height) mm from the central part of the molded product was cured for one day at a temperature of 25 ° C and a humidity of 60%. Four were obtained. About this sample piece, it measured based on the test method of the core density of JIS A 9511 (1995 edition).

<Measurement method of compression hardness>
About the sample piece which measured the core density, it measured based on the test method of the compression hardness of JIS A 9511 (1995 edition).

<Method of measuring flammability (burning distance)>
Five sample pieces of 150 (length) x 50 (width) x 13 (height) mm were obtained from the center of the molded product, and flammability was determined based on the flammability test method of JIS A 9511 (1995 edition). Was measured.

<Measurement method of flammability (time until combustion penetration)>
The polyurethane resin obtained by the above method is a sample of 200 (width) × 300 (length) × 30 (width) mm from the center of the molded product cured at a temperature of 25 ° C. and a humidity of 60% for 1 day. Three were obtained, the density (core density) was measured, and then the flame was applied to the sample piece with a torch burner, and the combustibility was measured by the following method.
[Time until combustion penetration (second)] was measured from the time when the flame was applied to the time when the flame penetrated to the back side of the sample piece. The distance from the crater of the torch burner to the sample piece is 100 mm, and the flame distance of the torch burner is about 150 mm. A flame temperature of about 1200 to 1500 ° C. was used.

As shown in Tables 1 to 3, the polyurethane resin of the present invention is a resin that is excellent in flammability even with a small amount of flame retardant, and in contrast when a polyol having the same average hydroxyl value is used, This resin is more excellent in compression hardness.

  The polyurethane resin of the present invention is excellent in flame retardancy, excellent in compression hardness and high in strength, and thus can be widely used for applications such as refrigerators, freezers, and building insulation.

Claims (8)

  A non-foamed or foamed polyurethane resin, wherein the concentration of the vinyl polymerizable functional group in the resin is 0.05 to 6 mmol / g. A non-foamed or foamed polyurethane resin is obtained by reacting an active hydrogen component (A) with an organic polyisocyanate (B). In (A), an active hydrogen-containing group and a vinyl represented by the following general formula (1) 1 or more active hydrogen compounds (a) selected from the following (a1) to (a3) having a polymerizable functional group, and optionally having a vinyl polymerizable functional group and no active hydrogen-containing group A resin containing at least one kind of compound (c) or containing (a) and / or (c) and at least one kind of active hydrogen compound (b) having no vinyl polymerizable functional group Item 1. A polyurethane resin according to Item 1.
(A1) Unsaturated carboxylic acid partial ester or partially unsaturated alkyl ether of polyol (a2) Unsaturated carboxylic acid partially amidated or partially unsaturated alkylated product of amine (a3) Unsaturated carboxylic acid partially thioester or partially unsaturated polyamine Alkyl thioether

[Wherein R represents hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms. ]   The polyurethane resin according to claim 2, wherein the active hydrogen compound (a) has an active hydrogen value of 10 to 1800.   The mass ratio of the active hydrogen compound (a) and the compound (c) in the active hydrogen component (A) to the active hydrogen compound (b) is [(a) + (c)] :( b) = 0.5 The polyurethane resin according to claim 2 or 3, wherein: 99.5 to 100: 0.   The organic polyisocyanate (B) is mainly composed of at least one selected from 2,4'- and / or 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and modified products thereof. 4. The polyurethane resin according to any one of 4 above.   The polyurethane resin according to any one of claims 1 to 5, which has an aromatic ring concentration of 1 to 10 mmol / g.   The polyurethane resin according to any one of claims 2 to 6, which has a structure in which a vinyl polymer chain portion formed by polymerization of a vinyl polymerizable functional group is crosslinked to a polyurethane chain portion formed by a polyurethane formation reaction.   The polyurethane resin according to any one of claims 2 to 7, which is a foamed polyurethane resin obtained by reacting an active hydrogen component (A) with an organic polyisocyanate (B) in the presence of a foaming agent (C).