JP2022081256A - Polyisocyanate composition and resin composition - Google Patents

Abstract

To provide a polyisocyanate composition excellent in compatibility to a main agent under a low temperature environment of about -10°C, and excellent in flexibility at a low temperature of about -10°C and at normal temperature of about 23°C when formed into a coating film.SOLUTION: A polyisocyanate composition is derived from at least one diisocyanate selected from the group consisting of aliphatic diisocyanate and alicyclic diisocyanate, polycaprolactone polyol (A) and polyether polyol (B); polypropylene glycol of 20 pts.mass or larger is contained for 100 pts.mass of the polyether polyol (B).SELECTED DRAWING: None

Description

The present invention relates to polyisocyanate compositions and resin compositions.

In recent years, with regard to curable polyurethane, in order to achieve coating film physical properties that cannot be solved by conventional curing agents, higher quality and higher performance of the curing agent have been increasing as market needs. In particular, in coating films, pressure-sensitive adhesives, adhesives, sealings, etc. that develop final physical properties by curing, further development is required because the performance derived from the curing agent greatly contributes. In particular, as a market trend, there is a tendency that high flexibility of the cured composition is required.

Patent Documents 1 and 2 disclose polyisocyanate compositions modified with polyester polyols or polyether polyols. It is disclosed that the coating film formed by blending the composition is excellent in extensibility and bending resistance.

Japanese Unexamined Patent Publication No. 61-28518 Japanese Unexamined Patent Publication No. 2-1718

There is a demand for a polyisocyanate composition that can obtain a coating film that is more flexible than the polyisocyanate compositions described in Patent Documents 1 and 2 in a harsh environment, specifically at a low temperature of about -10 ° C. There is.

The present invention has been made in view of the above circumstances, has good compatibility with the main agent in a low temperature environment of about -10 ° C, and has a low temperature of about -10 ° C and 23 when used as a coating film. Provided is a polyisocyanate composition having excellent flexibility at room temperature of about ° C. Further, a resin composition using the polyisocyanate composition is provided.

That is, the present invention includes the following aspects.
(1) Derived from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and polycaprolactone polyols (A) and polyether polyols (B).
A polyisocyanate composition containing 20 parts by mass or more of polypropylene glycol with respect to 100 parts by mass of the polyether polyol (B).
(2) The number average molecular weight of the polycaprolactone polyol (A) is 500 or more and 1500 or less, and
The polyisocyanate composition according to (1), wherein the polyether polyol (B) has a number average molecular weight of 1000 or more and 7000 or less.
(3) The polyisocyanate composition according to (2), wherein the weight ratio of the polytetramethylene ether glycol to the polypropylene glycol in the polyether polyol (B) is 0/100 or more and 60/40 or less.
(4) One of (1) to (3), wherein the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl group of the polycaprolactone polyol (A) and the polyether polyol (B) is 2 or more and 10 or less. The polyisocyanate composition described.
(5) The polyisocyanate according to any one of (1) to (4), wherein the mass ratio of the polycaprolactone polyol (A) to the polyether polyol (B) is 10/90 or more and 90/10 or less. Composition.
(6) A resin composition containing the polyisocyanate composition according to any one of (1) to (5) and a polyol.
(7) The resin composition according to (6), which is a pressure-sensitive adhesive composition.

According to the polyisocyanate composition of the above aspect, the compatibility with the main agent in a low temperature environment of about -10 ° C is good, and at a low temperature of about -10 ° C and a normal temperature of about 23 ° C when the coating film is formed. It is possible to provide a polyisocyanate composition having excellent flexibility. The resin composition of the above aspect contains the polyisocyanate composition and is excellent in flexibility at a low temperature of about −10 ° C. and a normal temperature of about 23 ° C. when formed into a coating film.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be modified in various ways without departing from the gist thereof.

In addition, in this specification, a "polyol" means a compound which has two or more hydroxy groups (-OH) in one molecule.
Further, in the present specification, "polyisocyanate" means a reaction product in which a plurality of monomer compounds having two or more isocyanate groups (-NCO) are bonded.
Further, in the present specification, unless otherwise specified, "(meth) acrylic" includes methacrylic and acrylic, and "(meth) acrylate" includes methacrylate and acrylate.

≪Polyisocyanate composition≫
The polyisocyanate composition of the present embodiment is derived from a diisocyanate and a polycaprolactone polyol (A) and a polyether polyol (B). That is, the polyisocyanate composition of the present embodiment is a reaction product of diisocyanate with the polycaprolactone polyol (A) and the polyether polyol (B), and is modified with the polycaprolactone polyol (A) and the polyether polyol (B). It contains the polyisocyanate produced. The diisocyanate is at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
The polyisocyanate composition of the present embodiment contains 20 parts by mass or more of polypropylene glycol with respect to 100 parts by mass of the polyether polyol (B).

As described above, the polyisocyanate composition of the present embodiment exhibits higher flexibility than the conventional one by using two different polyols and containing polypropylene glycol as the polyether polyol (B), and specifically. Has good compatibility with the main agent in a low temperature environment of about −10 ° C., and a coating film having excellent flexibility at a low temperature of about −10 ° C. and a normal temperature of about 23 ° C. can be obtained.

Next, each component of the polyisocyanate composition of the present embodiment will be described in detail below.

<Polyisocyanate>
The polyisocyanate composition of the present embodiment may be a polyisocyanate having all the structural units derived from the diisocyanate, the polycaprolactone polyol (A) and the polyether polyol (B) in one molecule, and the diisocyanate may be contained in one molecule. , A mixture of polyisocyanates having a structural unit derived from at least one selected from the group consisting of polycaprolactone polyol (A) and polyether polyol (B).

The polyisocyanate can have at least one structure selected from the group consisting of an allophanate structure, a uretdione structure, an iminooxadiazinedione structure, an isocyanurate structure, a urea structure, a urethane structure, and a biuret structure. Above all, it is preferable to have at least one structure selected from the group consisting of a urethane structure, an allophanate structure, a biuret structure, a urea structure, and an isocyanurate group.

[Diisocyanate]
The diisocyanate is at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.

The aliphatic diisocyanate is not limited to the following, and is, for example, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, ethyl (2,6-diisocyanato) hexanoate, 1,6-diisocyanate. Natohexane (hereinafter sometimes abbreviated as "HDI"), 1,9-diisocyanatononan, 1,12-diisocyanatododecane, 2,2,4- or 2,4,4-trimethyl-1 , 6-Diisocyanatohexane and the like. These aliphatic diisocyanates may be used alone or in combination of two or more.

The alicyclic diisocyanate is not limited to the following, but for example, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (hereinafter, may be abbreviated as "hydrogenated XDI"), 1 , 3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl1-isocyanato-3- (isocyanatomethyl) cyclohexane (hereinafter, may be abbreviated as "IPDI"), 4-4' -Diisocyanato-dicyclohexylmethane (hereinafter, may be abbreviated as "hydrogenated MDI"), 2,5- or 2,6-diisocyanatomethylnorbornane and the like can be mentioned. These alicyclic diisocyanates may be used alone or in combination of two or more.

Any of these aliphatic diisocyanates and alicyclic diisocyanates may be used alone, or two or more kinds of aliphatic diisocyanates and alicyclic diisocyanates may be used in combination.

Among them, as the diisocyanate, HDI, IPDI, hydrogenated XDI, or hydrogenated MDI is preferable, HDI or IPDI is more preferable, and HDI is further preferable.

In addition to the above-mentioned diisocyanate, an isocyanate monomer as shown below may be further used for producing the polyisocyanate.
(1) Aromatic diisocyanates such as diphenylmethane-4,4'-diisocyanate (MDI), 1,5-naphthalenediocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate, m-tetramethylxylylene diisocyanate (TMXDI).
(2) 4-Isocyanate Methyl-1,8-octamethylene diisocyanate (hereinafter, may be referred to as "NTI"), 1,3,6-hexamethylene triisocyanate (hereinafter, may be referred to as "HTI"). , Bis (2-isocyanatoethyl) 2-isocyanatoglutarate (hereinafter, may be referred to as "GTI"), lysine triisocyanate (hereinafter, may be referred to as "LTI") and the like.

<Polycaprolactone polyol (A)>
The polycaprolactone polyol is not particularly limited, but specifically, it can be obtained by ring-opening polymerization in the presence of a catalyst using ε-caprolactone as a divalent or higher valent, preferably a trivalent alcohol as an initiator. Such an initiator is not particularly limited, but specifically, a dihydric alcohol such as ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentylbricol; or a trihydric alcohol such as trimethylolpropane or glycerin. Alcohol or the like is used. In terms of obtaining a low-viscosity polyisocyanate, a polycaprolactone polyol having a branch is preferable. Such polycaprolactone polyols can be obtained by using a trihydric or higher alcohol as an initiator.

The catalyst is not particularly limited, but specifically, an organic titanium compound such as tetrabutyl titanate, tetrapropyl titanate, or tetraethyl titanate; tin octylate, dibutyltin oxide, dibutyltin laurate, stannous chloride, and bromide. A tin compound such as arsenic is used.

The ring-opening polymerization of ε-caprolactone is not particularly limited, but specifically, the molar ratio of ε-caprolactone to the above-mentioned initiator is set so as to have a desired molecular weight under a nitrogen gas atmosphere, and further, ε- It can be carried out by adding a catalyst of 0.1% by mass or more and 100% by mass or less to caprolactone and reacting at a temperature of 150 ° C. or more and 200 ° C. or less for 4 hours or more and 10 hours or less.

In the polyisocyanate, a urethane group is formed by the reaction of the hydroxyl group of the polycaprolactone polyol (A) with the isocyanate group of the diisocyanate.

The average number of hydroxyl group functional groups of the polycaprolactone polyol (A) is preferably 2.0 or more and 8.0 or less, more preferably 2 or more and 6 or less, further preferably 2 or more and 5 or less, and particularly preferably 3. The average number of hydroxyl group functional groups of the polycaprolactone polyol (A) referred to here is the number of hydroxyl groups present in one molecule of the polycaprolactone polyol (A).

The number average molecular weight of the polycaprolactone polyol (A) is preferably 500 or more and 1500 or less, more preferably 600 or more and 1400 or less, further preferably 700 or more and 1300 or less, and particularly preferably 850 or more and 1250 or less.
When the number average molecular weight of the polycaprolactone polyol (A) is within the above range, the obtained coating film is more excellent in flexibility at low temperature and normal temperature. The number average molecular weight Mn of the polycaprolactone polyol (A) is, for example, a polystyrene-based number average molecular weight measured by gel permeation chromatography (GPC).

Examples of commercially available polycaprolactone polyols include the trade names "Plaxel 305" (number average molecular weight 550), "Plaxel 308" (number average molecular weight 850), and "Pluxel 309" (number average molecular weight 900) manufactured by Daicel. , "Plaxel 312" (number average molecular weight 1250), "Plaxel 205" (number average molecular weight 530), "Plaxel 210" (number average molecular weight 1000); trade name "Polylite OD-X-2735" manufactured by DIC Co., Ltd. (Number average molecular weight 500), "Polylite OD-X-2586" (number average molecular weight 850), "Polylite OD-X-2588" (number average molecular weight 1250) and the like can be mentioned.

<Polyether polyol (B)>
The polyether polyol (B) contains polypropylene glycol (PPG, also referred to as polyoxypropylene polyol).
The content of PPG with respect to 100 parts by mass of the polyether polyol (B) in the polyisocyanate composition of the present embodiment is 20 parts by mass or more, preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and 55 parts by mass. More than parts are more preferable, 60 parts by mass is particularly preferable, and 100 parts by mass is most preferable. When the content of PPG is at least the above lower limit value, the compatibility with the main agent in a low temperature environment can be improved.

The polypropylene glycol is not particularly limited, but specifically, polyoxypropylene diol or triol; a so-called pluronic (registered trademark) type polyoxypropylene diol obtained by addition-polymerizing ethylene oxide at the end of polyoxypropylene diol or triol. Alternatively, triol; polyoxypropylene polyoxyethylene polymer diol, triol, or the like can be mentioned. Among these, the pluronic (registered trademark) type polyoxypropylene diol or triol is preferable because it has excellent reactivity with diisocyanate.

Examples of the method for producing polypropylene glycol include a method in which propylene oxide, if necessary, ethylene oxide or the like is added alone or as a mixture to an initiator and a catalyst. The initiator is not particularly limited, and specific examples thereof include polyhydric alcohols, polyhydric phenols, polyamines, alkanolamines, and mixtures thereof, and more specifically, ethylene glycol, diethylene glycol, and propylene glycol. Dihydric alcohols such as dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; diamines such as ethylenediamine; and mixtures thereof. Can be mentioned. The catalyst is not particularly limited, but specifically, hydroxides such as lithium, sodium and potassium; strongly basic catalysts such as alcoholate and alkylamine; metal porphyrin, complex metal cyan compound complex, metal and 3 Examples thereof include a complex with a chelating agent having a counterbore or higher, and a complex metal complex such as a zinc hexacyanocobalate complex. In addition, a method of dehydrating and condensing a polyhydric alcohol to obtain polypropylene glycol and the like can be mentioned.

As commercially available polypropylene glycols, the trade name "Exenol 510" (terminal EO addition type polyoxypropylene diol, number average molecular weight 4000) and "Exenol 840" (terminal EO addition type polyoxypropylene) manufactured by Asahi Glass Co., Ltd. are available. Triol, number average molecular weight 6500), "Exenol 1020" (terminal EO addition type polyoxypropylene diol, number average molecular weight 1000), "Exenol 2020" (terminal EO addition type polyoxypropylene diol, number average molecular weight 2000), etc. Can be mentioned.

The polyether polyol (B) can contain other polyether polyols in addition to polypropylene glycol.
The other polyether polyol is not particularly limited, but for example, an alkali metal hydroxide or a strongly basic catalyst is used to add the alkylene oxide alone or the mixture to the polyhydric alcohol alone or the mixture. Examples thereof include a polyether polyol obtained by reacting a polyamine compound with an alkylene oxide, and a so-called polymer polyol obtained by polymerizing acrylamide or the like using the above-mentioned polyether as a medium.
Examples of the alkali metal include lithium, sodium, potassium and the like.
Examples of the strongly basic catalyst include alcoholates, alkylamines and the like.
The polyhydric alcohol is not particularly limited, and examples thereof include at least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, and glycerin.
Examples of the alkylene oxide include ethylene oxide, butylene oxide, cyclohexene oxide, styrene oxide and the like.
Examples of the polyamine compound include ethylenediamines.

Among them, as the other polyether polyol, polytetramethylene ether glycol (PTMG, also referred to as polyoxytetramethylene polyol) is preferable.

Polytetramethylene ether glycol is produced by cationic polymerization of tetrahydrofuran using a catalyst or the like. The catalyst to be used is not particularly limited, but specifically, acetic anhydride-perchloric acid, fluorosulfonic acid, fuming sulfuric acid and the like are used. For example, the production of polyoxytetremethylene glycol is not particularly limited, but specifically, a fluorosulfonic acid of about 1% by mass or more and 30% by mass or less is usually added to the raw material tetrahydrofuran to 5 ° C. or more and 65% by mass. It can be carried out under the condition that the reaction is carried out at a temperature of ° C. or lower for several minutes or more and several tens of hours or less. Further, it can be obtained by adding butylene oxide using a polyhydric alcohol or the like as an initiator and a strong basic catalyst or the like as in the above-mentioned method for producing polypropylene glycol. Further, the molecular weight of the produced polytetramethylene ether glycol is adjusted by changing the polymerization temperature, the polymerization time, the amount of the catalyst used, and the like.

Examples of commercially available polytetramethylene ether glycols include trade names "PTMG1000" (number average molecular weight 1000), "PTMG2000" (number average molecular weight 2000), and "PTMG3000" (number average molecular weight 2000) manufactured by Mitsubishi Chemical Corporation. 2900), "PTMG4000" (number average molecular weight 4000) and the like.

In the polyether polyol (B), the mass ratio of polytetramethylene ether glycol to polypropylene glycol (mass ratio of PTMG / PPG) is preferably 0/100 or more and 80/20 or less, and more preferably 0/100 or more and 60/40 or less. , 0/100 or more and 50/50 or less is more preferable, and 0/100 or more and 45/55 or less is particularly preferable.
When the mass ratio of PTMG / PPG is within the above range, the compatibility with the main agent in a low temperature environment can be improved.

The number average molecular weight of the polyether polyol (B) is preferably 1000 or more and 7,000 or less, more preferably 2000 or more and 7,000 or less, further preferably 3000 or more and 6700 or less, and 4000 or more and 6500 or less. It is particularly preferable to have.
When the number average molecular weight of the polyether polyol (B) is within the above range, the obtained coating film is more excellent in flexibility at low temperature and normal temperature. The number average molecular weight Mn of the polyether polyol (B) is, for example, a polystyrene-based number average molecular weight measured by GPC. When two or more kinds of the polyether polyol (B) are mixed and used, the number average molecular weight of the mixture is calculated.

In the polyisocyanate composition of the present embodiment, the mass ratio of the polycaprolactone polyol (A) to the polyether polyol (B) (mass ratio of (A) / (B)) is 10/90 or more and 90/10 or less. Is preferable, 15/85 or more and 85/15 or less is more preferable, and 18/82 or more and 83/17 or less is further preferable.
When the mass ratio of (A) / (B) is at least the above lower limit value, the compatibility with the main agent in a low temperature environment can be improved. On the other hand, when it is not more than the above upper limit value, a coating film having more excellent flexibility at low temperature and normal temperature can be obtained.
The mass ratio of (A) / (B) can be calculated from, for example, the blending amount of each polyol.

<Manufacturing method of polyisocyanate composition>
The polyisocyanate is obtained by reacting the above diisocyanate with the polycaprolactone polyol (A) and the polyether polyol (B). Hereinafter, the polycaprolactone polyol (A) and the polyether polyol (B) may be collectively referred to as a polyol.

The polycaprolactone polyol (A) and the polyether polyol (B) can be used alone or as a mixture, respectively. When used as a mixture, it may be mixed before reacting with diisocyanate, or each polyol may be independently reacted with diisocyanate to form polyisocyanate and then mixed.
That is, as a method for producing a polyisocyanate composition, for example, a method of simultaneously reacting a diisocyanate with a polycaprolactone polyol (A) and a polyether polyol (B) to obtain a polyisocyanate composition; a diisocyanate and a polycaprolactone. A method for obtaining a polyisocyanate composition by mixing a reaction with a polyol (A), a diisocyanate and a reaction with a polyether polyol (B); a diisocyanate and a polycaprolactone polyol (A) or Examples thereof include a method of reacting with the polyether polyol (B) and then further reacting with the remaining polyol to obtain a polyisocyanate composition.

The blending amount of the polycaprolactone polyol (A) and the polyether polyol (B) is preferably such that the mass ratio of the polycaprolactone polyol (A) to the polyether polyol (B) is within the above range.

The reaction between the polyol and the diisocyanate is carried out as follows. The reaction temperature is usually room temperature (about 23 ° C.) or higher and 200 ° C. or lower, preferably 80 ° C. or higher and 120 ° C. or lower. If the reaction temperature is at least the above lower limit, the reaction time will be shorter, while if it is at least the above upper limit, the increase in viscosity of the polyisocyanate due to an undesired side reaction can be further avoided, and the resulting polyisocyanate will be colored. It can be avoided more.

The reaction may be carried out without a solvent, or may be carried out with any solvent which is inert to the isocyanate group. If necessary, a known catalyst may be used in order to promote the reaction between the isocyanate group and the hydroxyl group.

At the time of the reaction, the molar ratio of the isocyanate group of the diisocyanate (the molar ratio of the hydroxyl group / isocyanate group) to the hydroxyl group of the polycaprolactone polyol (A) and the polyether polyol (B) is preferably 2 or more and 10 or less, preferably 3 or more and 9 or less. Is more preferable, and 4 or more and 8 or less are further preferable. When the molar ratio of the hydroxyl group / isocyanate group is at least the above lower limit value, it is possible to further avoid an increase in the viscosity of the polyisocyanate due to the sequential addition reaction between the diisocyanate and the polyol. On the other hand, when it is not more than the above upper limit value, the productivity becomes better.

At the end of the reaction, the unreacted diisocyanate in the reaction mixture is recovered by a known method such as a thin film distillation apparatus or solvent extraction. If the residual amount of unreacted diisocyanate is small, the odor, toxicity, irritation and the like caused by diisocyanate during heat curing can be further avoided.

<Physical characteristics of polyisocyanate composition>
The isocyanate group content (NCO group content) of the polyisocyanate composition of the present embodiment is 3% by mass or more and 8% by mass with respect to the total mass of the polyisocyanate composition in a state where it does not substantially contain a solvent or diisocyanate. % Or more, more preferably 3.1% by mass or more and 7.5% by mass or less, and even more preferably 3.3% by mass or more and 7.3% by mass or less.
The NCO group content can be determined, for example, by reacting the isocyanate group of the polyisocyanate composition with an excess amine (dibutylamine or the like) and back-titrating the remaining amine with an acid such as hydrochloric acid.

≪Resin composition≫
The resin composition of the present embodiment contains the above-mentioned polyisocyanate composition as a curing agent component and a polyol as a main agent component.

By containing the polyisocyanate composition as a curing agent component in the resin composition of the present embodiment, a coating film having excellent flexibility at a low temperature of about −10 ° C. and a normal temperature of about 23 ° C. can be obtained.

The resin composition of the present embodiment is, for example, a building paint, an automobile paint, an automobile repair paint, a plastic paint, an adhesive, an adhesive, a building material, a household water-based paint, other coating agents, a sealing agent, an ink, and the like. It can be used for casting materials, elastomers, foams, plastic raw materials, fiber treatment agents, etc.
Above all, the resin composition of the present embodiment is preferably used as a pressure-sensitive adhesive composition because it has good flexibility at low temperature and normal temperature, especially when it is used as a coating film.

Next, each component contained in the resin composition of the present embodiment will be described in detail below.

<Polyol>
Specific examples of the polyol include an aliphatic hydrocarbon polyol, a polyether polyol, a polyester polyol, an epoxy resin, a fluorine-containing polyol, and an acrylic polyol.
Above all, the polyol is preferably an acrylic polyol.

[Aliphatic hydrocarbon polyol]
Examples of the aliphatic hydrocarbon polyol include hydroxyl-terminated polybutadiene and its hydrogenated additive.

[Polyether polyol]
Examples of the polyether polyol include those obtained by using any of the following methods (1) to (3).
(1) A polyether polyol or a polytetramethylene ether glycol obtained by adding a alkylene oxide alone or a mixture to a polyhydric alcohol alone or a mixture.
(2) A polyether polyol obtained by reacting an alkylene oxide with a polyfunctional compound.
(3) A so-called polymer polyol obtained by polymerizing acrylamide or the like using the polyether polyol obtained in (1) or (2) as a medium.
Examples of the polyhydric alcohol include glycerin and propylene glycol.
Examples of the alkylene oxide include ethylene oxide and propylene oxide.
Examples of the polyfunctional compound include ethylenediamine and ethanolamine.

[Polyester polyol]
Examples of the polyester polyol include any of the following polyester polyols (1) and (2).
(1) A polyester polyol resin obtained by a condensation reaction between a dibasic acid alone or a mixture of two or more kinds and a polyhydric alcohol alone or a mixture of two or more kinds.
(2) A polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone with a polyhydric alcohol.
Examples of the dibasic acid include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic acid anhydride, isophthalic acid, terephthalic acid, and carboxylic acids such as 1,4-cyclohexanedicarboxylic acid.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, and pentaerythritol. , 2-Methylolpropanediol, ethoxylated trimethylolpropane and the like.

[Epoxy resin]
Examples of the epoxy resin include novolak type epoxy resin, β-methylepicro type epoxy resin, cyclic oxylan type epoxy resin, glycidyl ether type epoxy resin, glycol ether type epoxy resin, epoxy type aliphatic unsaturated compound, and epoxidized fatty acid ester. , Epoxy resins such as ester-type polyvalent carboxylic acids, aminoglycidyl-type epoxy resins, halogenated epoxy resins, resorcin-type epoxy resins, and resins obtained by modifying these epoxy resins with amino compounds, polyamide compounds, and the like.

[Fluorine-containing polyol]
Examples of the fluorine-containing polyol include fluoroolefins, cyclohexyl vinyl ethers, and hydroxyalkyls disclosed in Reference 1 (Japanese Patent Laid-Open No. 57-34107) and Reference 2 (Japanese Patent Laid-Open No. 61-275311). Examples thereof include copolymers such as vinyl ether and monocarboxylic acid vinyl ester.

[Acrylic polyol]
The acrylic polyol may, for example, polymerize a polymerizable monomer having one or more active hydrogens in one molecule, or may have a polymerizable monomer having one or more active hydrogens in one molecule, if necessary. It is obtained by copolymerizing the polymerizable monomer with another copolymerizable monomer.

Examples of the polymerizable monomer having one or more active hydrogens in one molecule include those shown in the following (i) to (iii). These may be used alone or in combination of two or more.
(I) Acrylic acid ester having active hydrogen such as -2-hydroxyethyl acrylate, -2-hydroxypropyl acrylate, and -2-hydroxybutyl acrylate.
(Ii) A methacrylic acid ester having active hydrogen such as -2-hydroxyethyl methacrylate, -2-hydroxypropyl methacrylate, and -2-hydroxybutyl methacrylate.
(Iii) A (meth) acrylic acid ester having a polyvalent active hydrogen such as acrylic acid monoester or methacrylic acid monoester of glycerin, acrylic acid monoester or methacrylic acid monoester of trimethylolpropane.

Examples of other monomers copolymerizable with the polymerizable monomer include those shown in the following (i) to (v). These may be used alone or in combination of two or more.
(I) Acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, -n-butyl acrylate, and -2-ethylhexyl acrylate.
(Ii) Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, and glycidyl methacrylate.
(Iii) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid.
(Iv) Unsaturated amides such as acrylamide, N-methylolacrylamide, and diacetoneacrylamide.
(V) Styrene, vinyltoluene, vinyl acetate, acrylonitrile, etc.

Further, an acrylic polyol obtained by copolymerizing a polymerizable ultraviolet stable monomer disclosed in Reference 3 (Japanese Patent Laid-Open No. 1-261409) and Reference Document 4 (Japanese Patent Laid-Open No. 3-006273). And so on.

Specifically, as the polymerizable ultraviolet stable monomer, for example, 4- (meth) acryloyloxy-2, 2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2, 2,6 , 6-Tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2, 2,6,6-tetramethylpiperidine, 2-hydroxy-4- (3-methacrylicoxy-2-hydroxypropoxy) benzophenone and the like. Be done.

For example, the above monomer component is solution-polymerized in the presence of a known radical polymerization initiator such as a peroxide or an azo compound, and if necessary, diluted with an organic solvent or the like to obtain an acrylic polyol. Can be done.

When an aqueous-based base acrylic polyol is obtained, it can be produced by a known method such as a method of solution-polymerizing an olefinically unsaturated compound to convert it into an aqueous layer or emulsion polymerization. In that case, water solubility or water dispersibility can be imparted by neutralizing an acidic portion such as a carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or a sulfonic acid-containing monomer with amine or ammonia.

[Isocyanate group / hydroxyl group]
The molar ratio of isocyanate groups (isocyanate group / hydroxyl group molar ratio) of the polyisocyanate composition to the hydroxyl groups of the polyol contained in the resin composition of the present embodiment is determined by the required physical properties of the resin film, but is usually determined. It is 0.01 or more and 22.5 or less.

<Other ingredients>
The resin composition of the present embodiment may further contain other additives.
Examples of other additives include curing agents other than polyisocyanate compositions that can react with polyols, curing catalysts, solvents, pigments (extension pigments, coloring pigments, metallic pigments, etc.), photopolymerization initiators, ultraviolet absorbers, and the like. Examples thereof include a light stabilizer, a radical stabilizer, an anti-yellowing agent that suppresses coloring during the baking process, a coating surface adjusting agent, a flow adjusting agent, a pigment dispersant, a defoaming agent, a thickener, and a film-forming auxiliary.

Examples of the curing agent include melamine resin, urea resin, epoxy group-containing compound or resin, carboxy group-containing compound or resin, acid anhydride, alkoxysilane group-containing compound or resin, hydrazide compound and the like.

The curing catalyst may be a basic compound or a Lewis acidic compound.
Examples of the basic compound include metal hydroxides, metal alkoxides, metal carboxylates, metal acetyl acetylates, hydroxides of onium salts, onium carboxylates, halides of onium salts, and metal salts of active methylene compounds. Examples thereof include onium salts of active methylene compounds, aminosilanes, amines, phosphins and the like. As the onium salt, an ammonium salt, a phosphonium salt or a sulfonium salt is suitable.
Examples of the Lewis acidic compound include an organic tin compound, an organic zinc compound, an organic titanium compound, and an organic zirconium compound.

Examples of the solvent include 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, and 3-methoxy-3-methyl. -1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether (DPDM), propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethanol, methanol , Iso-propanol, 1-propanol, iso-butanol, 1-butanol, tert-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butane Examples thereof include diol, 1,3-butanediol, ethyl acetate, isopropyl acetate, butyl acetate, toluene, xylene, pentane, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, and mineral spirit. These solvents may be used alone or in combination of two or more.

In addition, pigments (constitution pigments, coloring pigments, metallic pigments, etc.), UV absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface adjusting agents, flow adjusting agents, pigments As the dispersant, defoaming agent, thickening agent and film-forming auxiliary, known ones can be appropriately selected and used.

<Manufacturing method of resin composition>
The resin composition of the present embodiment can be produced by a conventionally known method.
When the resin composition of the present embodiment is a pressure-sensitive adhesive composition, for example, a general mixer such as a Banbury mixer, a single-screw screw extruder, a twin-screw screw extruder, a conider, or a multi-screw screw extruder is used. A method of melt-kneading, a method of dissolving or dispersing and mixing each component, a method of coating on a base film with a coater or the like, and then a method of removing the solvent by heating is used.

The resin composition of the present embodiment may be foamed in order to reduce the weight, make it flexible, and improve the adhesion. Examples of the foaming method include a chemical method, a physical method, and the use of a heat-expandable microballoon. Bubbles can be distributed inside the material by adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, a physical foaming agent, or the like, or by adding a heat-expandable microballoon.

Further, by adding a hollow filler (already inflated balloon), weight reduction, flexibility, and improvement of adhesion may be achieved.

When the resin composition of the present embodiment is an adhesive composition, a tackifier resin may be added for adjusting the adhesive force and the cohesive force. Examples of the tackifying resin include a rosin-based tackifier resin, a terpene-based tackifier resin, a petroleum-based tackifier resin, and a styrene-based tackifier resin. These tackifier resins may be used alone or in combination of two or more. Further, the softening point of the tackifier resin is preferably 90 ° C. or higher and 160 ° C. or lower.

Hereinafter, the present embodiment will be described in more detail based on Examples and Comparative Examples, but the present embodiment is not limited to the following Examples.

<Test items>
The polyisocyanate compositions produced in Examples and Comparative Examples were measured and evaluated for their physical properties according to the methods shown below.

[Physical characteristics 1]
(Isocyanate group (NCO) content)
First, 2 g or more and 3 g or less of the measurement sample were precisely weighed in a flask (Wg). Then, 20 mL of toluene was added to dissolve the measurement sample. Then, 20 mL of a toluene solution of 2N-butylamine was added, and after mixing, the mixture was allowed to stand at room temperature for 15 minutes. Then 70 mL of isopropyl alcohol was added and mixed. This solution was then titrated into an indicator with a 1N hydrochloric acid solution (Factor F). The obtained titration value was V2 mL. Then, without the polyisocyanate sample, the obtained titration value was set to V1 ml. Next, the isocyanate group (NCO) content (NCO%) (mass%) of the polyisocyanate was calculated from the following formula.

Isocyanate group (NCO) content (% by mass) = (V1-V2) x F x 42 / (W x 1000) x 100

[Physical characteristics 2]
(Number average molecular weight)
The number average molecular weight is a polystyrene-based number average molecular weight measured by gel permeation chromatography (GPC) using the following apparatus.

(Measurement condition)
Equipment: HLC-802A manufactured by Tosoh Corporation
Column: Made by Tosoh Corporation, G1000HXL x 1
G2000HXL x 1
G3000HXL x 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer

[Preparation of resin composition]
Each polyisocyanate composition and an acrylic polyol (manufactured by Allnex, trade name "Setalux 1152") are mixed so that the molar ratio of isocyanate groups to hydroxyl groups is 1.0, and the solid content becomes 50% by mass. Diluted with butyl acetate. Next, a tin catalyst (manufactured by Nitto Kasei Co., Ltd., trade name "Neostan U-100") was further mixed with the diluted solution in an amount of 300 mass ppm with respect to the solid content to obtain each resin composition.

[Evaluation 1]
(Compatibility with the main agent)
Immediately after preparation, each resin composition was kept in an environment of −10 ° C. for 5 days. The state of the coating liquid was visually observed and evaluated according to the following evaluation criteria.

(Evaluation criteria)
⊚: Transparent and uniform △: Partially turbid ×: Overall turbidity

[Preparation of coating film]
Each resin composition was applied onto a polypropylene plate so as to have a film thickness of 30 μm, and dried by heating at 120 ° C. for 30 minutes. Then, each coating film was prepared by drying at 23 ° C. and 50% humidity environment for 1 day.

[Evaluation 2]
(Low temperature breaking elongation)
The prepared coating film was cut into strips to prepare test pieces. Next, it was mounted on a tensile tester (Tensilon universal tester) so as to have a length of 20 mm and a width of 10 mm, and a test was carried out at a tensile speed of 20 mm / min at a test temperature of -10 ° C. .. The fractured elongation was evaluated according to the following evaluation criteria.

(Evaluation criteria)
⊚: Breaking elongation 150% or more ○: Breaking elongation 100% or more and less than 150% ×: Breaking elongation less than 100%

[Evaluation 3]
(Low temperature and low stress (stress at 20% elongation))
The prepared coating film was cut into strips to prepare test pieces. Next, it was mounted on a tensile tester (Tensilon universal tester) so as to have a length of 20 mm and a width of 10 mm, and the test was carried out at a test temperature of −10 ° C. and a tensile speed of 20 mm / min. The stress values at an elongation of 20% were evaluated according to the following evaluation criteria.

(Evaluation criteria)
⊚: less than 10 MPa ○: 10 MPa or more and less than 30 MPa ×: 30 MPa or more

[Evaluation 4]
(Low stress at room temperature (stress at elongation 75%))
The prepared coating film was cut into strips to prepare test pieces. Next, it was mounted on a tensile tester (Tensilon universal tester) so as to have a length of 20 mm and a width of 10 mm, and the test was carried out at a test temperature of 23 ° C. and a tensile speed of 20 mm / min. The stress values at an elongation of 75% were evaluated according to the following evaluation criteria.

(Evaluation criteria)
⊚: less than 2 MPa ○: 2 MPa or more and less than 5 MPa ×: 5 MPa or more

<Manufacturing of polyisocyanate composition>
[Example 1]
(Production of Polyisocyanate Composition PA-a1)
The inside of a 4-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel is made into a nitrogen atmosphere, and HDI 1000 g and a trifunctional polycaprolactone polyol (manufactured by DIC Co., Ltd., trade name "OD-" X2588 ”, number average molecular weight 1250) 496.0 g was charged, and the temperature inside the reactor was maintained at 100 ° C. under stirring to proceed with the urethanization reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain a polyisocyanate precursor. 100.0 g of the polyisocyanate precursor was charged in a flask, 57.0 g of polyoxypropylene diol (manufactured by AGC Co., Ltd., trade name "Exenol 510", number average molecular weight 4000) was charged, and the temperature inside the reactor was set to 100 ° C. under stirring. It was retained and the urethanization reaction was allowed to proceed to obtain a polyisocyanate composition PA-a1.

[Examples 2 to 6]
(Production of Polyisocyanate Compositions PA-a2-PA-a6)
Each polyisocyanate composition was obtained by the same method as in Example 1 except that the compositions shown in Table 1 were used.

[Example 7]
(Production of Polyisocyanate Composition PA-a7)
The inside of a four-necked flask equipped with a stirrer, a thermometer, a reflux cooling tube, a nitrogen blowing tube, and a dropping funnel is made into a nitrogen atmosphere, and HDI 1000 g, a trifunctional polycaprolactone polyol (manufactured by DIC Co., Ltd., trade name "OD-X2735") , Number average molecular weight 500) 150.0 g, Polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, trade name "PTMG1000", number average molecular weight 1000) 200.0 g, and polyoxypropylene diol (manufactured by AGC Co., Ltd., The product name "Excell 510", number average molecular weight 4000) 300.0 g was charged, and the temperature inside the reactor was maintained at 100 ° C. under stirring to proceed with the urethanization reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain a polyisocyanate composition PA-a6.

[Example 8 and Comparative Examples 1 to 3]
(Production of Polyisocyanate Compositions PA-a8 and PA-b1 to PA-b3)
Each polyisocyanate composition was obtained by the same method as in Example 7 except that the compositions shown in Table 2 were used.

Tables 1 and 2 show the physical characteristics of each of the obtained polyisocyanate compositions and the evaluation results using the method described above.

In addition, in Table 1 and Table 2, each abbreviation indicates the following compound.

(Polycaprolactone polyol (A))
A: Polycaprolactone polyol OD-X-2735: DIC Corporation, trifunctional polycaprolactone polyol, number average molecular weight 500
OD-X-2586: Trifunctional polycaprolactone polyol manufactured by DIC Corporation, number average molecular weight 850
OD-X-2588: Trifunctional polycaprolactone polyol manufactured by DIC Corporation, number average molecular weight 1250

(Polyether polyol (B))
B1: Polypropylene glycol Excelnol 510: Polyoxypropylene diol manufactured by AGC Inc., number average molecular weight 4000
Excelcol 840: AGC Inc., polyoxypropylene triol, number average molecular weight 6500
Excelnol 1020: manufactured by AGC Inc., polyoxypropylene diol, number average molecular weight 1000

B2: Other polyether polyols PTMG1000: Made by Mitsubishi Chemical Corporation, polytetramethylene ether glycol, number average molecular weight 1000

A polyisocyanate composition derived from a diisocyanate, a polycaprolactone polyol (A), and a polyether polyol (B), and containing 20 parts by mass or more of polypropylene glycol with respect to 100 parts by mass of the polyether polyol (B). PA-a1 to PA-a8 (Examples 1 to 8) have good compatibility with the main agent in a low temperature environment of about -10 ° C, and at a low temperature of about -10 ° C when used as a coating film. It was excellent in breaking elongation and low stress property at a low temperature of about -10 ° C and a normal temperature of about 23 ° C.

The polyisocyanate composition PA-b1 (Comparative Example 1) derived from the diisocyanate and the polycaprolactone polyol (A) had good compatibility with the main agent in a low temperature environment of about -10 ° C. The elongation at break at a low temperature of about −10 ° C. and the low stress property at a low temperature of about −10 ° C. and a normal temperature of about 23 ° C. when made into a coating film were poor.
Further, the polyisocyanate composition PA-b2 (Comparative Example 2) derived from the diisocyanate, the polycaprolactone polyol (A), and the polyether polyol (B) containing no polypropylene glycol was used as a coating film. The break elongation at a low temperature of about -10 ° C and the low stress resistance at a low temperature of about -10 ° C and a normal temperature of about 23 ° C were within the allowable range, but in a low temperature environment of about -10 ° C. The compatibility with the main agent was poor.
Further, polypropylene derived from the diisocyanate, the polycaprolactone polyol (A), and the polyether polyol (B), and less than 20 parts by mass (10 parts by mass) with respect to 100 parts by mass of the polyether polyol (B). In the polyisocyanate composition PA-b3 containing glycol (Comparative Example 3), the elongation at break at a low temperature of about -10 ° C when used as a coating film, and at a low temperature of about -10 ° C and a normal temperature of about 23 ° C. The low stress property was within the permissible range, but the compatibility with the main agent in a low temperature environment of about −10 ° C. was poor.

According to the polyisocyanate composition of the present embodiment, the compatibility with the main agent in a low temperature environment of about -10 ° C is good, and the low temperature of about -10 ° C and the normal temperature of about 23 ° C when used as a coating film are obtained. It is possible to provide a polyisocyanate composition having excellent flexibility in the above.

Claims (7)

Derived from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and polycaprolactone polyols (A) and polyether polyols (B).
A polyisocyanate composition containing 20 parts by mass or more of polypropylene glycol with respect to 100 parts by mass of the polyether polyol (B). The number average molecular weight of the polycaprolactone polyol (A) is 500 or more and 1500 or less, and
The polyisocyanate composition according to claim 1, wherein the polyether polyol (B) has a number average molecular weight of 1000 or more and 7000 or less. The polyisocyanate composition according to claim 2, wherein in the polyether polyol (B), the mass ratio of polytetramethylene ether glycol to polypropylene glycol is 0/100 or more and 60/40 or less. The polyisocyanate composition according to any one of claims 1 to 3, wherein the molar ratio of the isocyanate group of the diisocyanate to the hydroxyl groups of the polycaprolactone polyol (A) and the polyether polyol (B) is 2 or more and 10 or less. thing. The polyisocyanate composition according to any one of claims 1 to 4, wherein the mass ratio of the polycaprolactone polyol (A) to the polyether polyol (B) is 10/90 or more and 90/10 or less. A resin composition comprising the polyisocyanate composition according to any one of claims 1 to 5 and a polyol. The resin composition according to claim 6, which is a pressure-sensitive adhesive composition.