JP5142820B2 - One-part curable solventless adhesive - Google Patents

Description

  The present invention relates to a one-component curable solventless adhesive, and more particularly to a one-component curable solventless adhesive used as a reactive hot melt adhesive.

  The reactive hot melt adhesive is generally prepared based on a urethane prepolymer having an isocyanate group at the molecular end, which is obtained by reacting a polyisocyanate component and a polyester polyol component. Such reactive hot melt adhesives are solid at room temperature, and are used for bonding various adherends by melting by heating and curing by moisture.

For example, a reactive hot melt adhesive comprising a polyisocyanate component and a polyol component in order to provide a reactive hot melt adhesive that improves dry cleaning resistance and washing resistance and can be used for fiber materials. In Japanese Patent Laid-Open No. 2004-26883, it has been proposed that a polyolefin-based polyol, a xylene resin, a rosin, a polyester polyol and a polyether polyol are contained as essential components as a polyol component (see, for example, Patent Document 1).
JP 2005-290280 A

However, when white or light-colored fibers are pasted together using the reactive hot melt adhesive described in Patent Document 1, there is a problem that the pasted fibers turn yellow over time due to sunlight or light from a fluorescent lamp. .
In addition, when bleaching with an alkaline bleaching agent, the adhesive layer to which the fibers are bonded is yellowed, the appearance of the bonded fibers is impaired, and further, the bonding strength of the bonded fibers is reduced. .

  An object of the present invention is to provide a one-component curable solventless adhesive capable of suppressing yellowing over time and improving alkali resistance.

  In order to achieve the above object, the one-component curable solventless adhesive of the present invention is a one-component curable solventless adhesive obtained by reacting a polyisocyanate component and a polyol component, The component is at least one selected from the group consisting of aliphatic polyisocyanates, araliphatic polyisocyanates, and derivatives thereof, and is characterized by containing titanium oxide.

In the one-component curable solventless adhesive of the present invention, the content of titanium oxide is preferably 5 to 45% by weight.
In the one-component curable solventless adhesive of the present invention, the polyisocyanate component includes a derivative of an aliphatic polyisocyanate and / or an araliphatic polyisocyanate, and the derivative is an allophanate derivative and / or an isocyanurate derivative. Preferably it is.

In the one-component curable solventless adhesive of the present invention, it is preferable that the remaining amount of the polyisocyanate monomer is less than 1% by weight.
The one-component curable solventless adhesive of the present invention is preferably used for bonding fibers at least.

According to the one-component curable solventless adhesive of the present invention, it is possible to suppress yellowing of bonded fibers over time, and to improve alkali resistance. A decrease in strength can be suppressed.
Therefore, the one-component curable solventless adhesive of the present invention is suitably used as a reactive hot melt adhesive for bonding fibers.

The one-component curable solventless adhesive of the present invention is a reactive hot melt adhesive, and contains a urethane prepolymer having an isocyanate group at the molecular end as a main component. A urethane prepolymer is obtained by reacting a polyisocyanate component and a polyol component.
In the present invention, the polyisocyanate component is selected from polyisocyanate monomers such as aliphatic polyisocyanates and araliphatic polyisocyanates, and / or derivatives thereof.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate (TMDI), hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, 2, And aliphatic diisocyanates such as 4,4- or 2,2,4-trimethylhexamethylene diisocyanate.

Moreover, as aliphatic polyisocyanate, alicyclic polyisocyanate is mentioned, for example.
Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4 '-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate or mixtures thereof _(H 12 MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, And alicyclic diisocyanates such as 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (H ₆ XDI) or norbornane diisocyanate (NBDI). The

Among these, Preferably, an aliphatic diisocyanate is mentioned.
Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), ω, ω′-diisocyanate-1,4-diethylbenzene and the like. Preferably, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI) is used.

  The derivative of the polyisocyanate monomer is a derivative of an aliphatic polyisocyanate and / or an araliphatic polyisocyanate, for example, a large amount of the above-mentioned polyisocyanate component (ie, aliphatic polyisocyanate and / or araliphatic polyisocyanate). Isomers (dimers, trimers (eg, isocyanurate derivatives), pentamers, heptamers, etc.), biuret derivatives (eg, biuret derivatives produced by the reaction of the above polyisocyanate components with water) , Allophanate derivatives (for example, allophanate derivatives produced by the reaction of the above-described polyisocyanate component and monool or polyhydric alcohol (described later)), polyol derivatives (for example, the above-described polyisocyanate component and low molecular weight polyol (described later) Polyol derivatives produced by the reaction with), urea derivatives (eg urea derivatives produced by the reaction of the above polyisocyanate components and diamines), oxadiazine triones (eg, the above polyisocyanate components and carbon dioxide) And carbodiimide derivatives (such as carbodiimide derivatives generated by the decarboxylation condensation reaction of the polyisocyanate component described above). Of the derivatives, isocyanurate derivatives, allophanate derivatives, and isocyanurate / allophanate derivatives in which isocyanurate derivatives and allophanate derivatives are mixed are preferable.

These polyisocyanate components can be used alone or in combination of two or more.
The average number of functional groups of the polyisocyanate component is, for example, 3 or less, preferably 2.8 or less.
If the average number of functional groups of the polyisocyanate component exceeds 3, the viscosity of the urethane prepolymer increases, which may hinder workability and may decrease the thermal stability.

In the present invention, examples of the polyol component include macro polyols and low molecular weight polyols.
The macropolyol is a polyol having a number average molecular weight of 400 to 10,000, and examples thereof include polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like.

The polyester polyol can be obtained by a known esterification reaction, that is, a condensation reaction between a polybasic acid and a polyhydric alcohol, a transesterification reaction between an alkyl ester of a polybasic acid and a polyhydric alcohol, or the like.
Examples of the polybasic acid or its alkyl ester include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer acid, for example, fatty acids such as hexahydrophthalic acid and tetrahydrophthalic acid. Cyclic dicarboxylic acids such as aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid, or dialkyl esters thereof (for example, C 1-6 alkyl esters) or acid anhydrides thereof Or a mixture thereof. Preferably, isophthalic acid, phthalic acid, terephthalic acid, adipic acid, sebacic acid, etc. are mentioned.

  Examples of the polyhydric alcohol include alkanediols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, and 1,5-pentanediol. 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3,3′-dimethylolheptane, 1,9-nonane Diol, 1,10-decane diol, 12-hydroxystearyl alcohol, hydrogenated dimer diol, etc., C2-C40 alkane or aliphatic low molecular weight diol, etc., polyoxyalkylene glycol (for example, diethylene glycol, triethylene glycol, poly Oxyethylene glycol, zip Pyrene glycol, trioxypropylene glycol, polyoxypropylene glycol, poly (oxycarbon number 2-4 alkylene) glycol such as polyoxytetramethylene glycol or a copolymer of carbon number 2-4 alkylene oxide), bisphenol A or water Examples thereof include an alkylene oxide adduct of bisphenol A, a trihydric or higher polyhydric alcohol (for example, glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc.), or a mixture thereof. Polyhydric alcohols also include ester glycols such as neopentyl glycol hydroxypivalate.

Preferably, the polyester polyol includes an amorphous polyester polyol. Specifically, the polyester polyol is obtained by a condensation reaction between an aliphatic dicarboxylic acid and / or an aromatic dicarboxylic acid and an alkanediol (including ester glycol). A condensate is mentioned.
The polyether polyol is, for example, an alkylene oxide having a low molecular weight polyol as an initiator (for example, an alkylene oxide having 2 to 5 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, or oxetane compound). Can be obtained by ring-opening homopolymerization or ring-opening copolymerization. As the polyether polyol, preferably, polypropylene glycol is used.

The polycarbonate polyol can be obtained, for example, by reacting phosgene, dialkyl carbonate, diallyl carbonate, alkylene carbonate or the like in the presence or absence of a catalyst using a low molecular weight polyol as an initiator.
In addition, the polyurethane polyol is a polyester polyol, polyether polyol and / or polycarbonate polyol obtained as described above, in a ratio in which the equivalent ratio of hydroxyl group to isocyanate group (OH / NCO) exceeds 1, By making it react, it can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, or a polyester polyether polyurethane polyol.

  These macropolyols preferably include polyester polyols and polyether polyols. These macropolyols can be used alone or in combination of two or more. Preferably, polyester polyol (non-crystalline polyester polyol) and polyether polyol are used in combination. When these are used in combination, the polyether polyol is used in combination of, for example, 10 to 300 parts by weight, preferably 20 to 200 parts by weight, with respect to 100 parts by weight of the polyester polyol. By blending the polyether polyol with the polyester polyol, the viscosity of the one-part curable solventless adhesive can be adjusted to be low so that it can be easily applied to the substrate.

The hydroxyl equivalent of the macropolyol is, for example, 200 to 5000, and preferably 250 to 4000.
Moreover, the number average molecular weight of a macropolyol is 400-10000, for example, Preferably it is 500-8000.
The number average molecular weight of the macropolyol can be calculated from a known hydroxyl value measurement method such as an acetylation method or a phthalation method, and the number of functional groups of the initiator or the raw material.

  The low molecular weight polyol is a polyol having a number average molecular weight of less than 400, for example, ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexane. Diol, neopentyl glycol, alkane (carbon number 7 to 22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanedimethanol, alkane-1,2-diol (carbon number 17 to 20), hydrogenated bisphenol A, Low molecular weight diols such as 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, 2,2-bis (hydroxy 4 or more of low molecular weight triols such as methyl) -3-butanol and other aliphatic triols (8 to 24 carbon atoms), for example, tetramethylolmethane, D-sorbitol, xylitol, D-mannitol, D-mannitol, etc. And low molecular weight polyols having a hydroxyl group. These low molecular weight polyols can be used alone or in combination of two or more.

These polyol components can be used alone or in combination of two or more. Preferably, a macro polyol is used.
And a polyisocyanate component and a polyol component are made to react and a urethane prepolymer is obtained.
In order to synthesize the urethane prepolymer, the polyol component and the polyisocyanate component are mixed and reacted so that the isocyanate group of the polyisocyanate component is excessive with respect to the hydroxyl group of the polyol component.

More specifically, for example, the polyol component and the polyisocyanate component have an isocyanate group-to-hydroxyl group equivalent ratio R (NCO / OH) of, for example, exceeding 1, preferably 1.1 to 8.0. More preferably, the reaction is performed at a rate of 1.2 to 5.0, for example, at a reaction temperature of 50 to 140 ° C., for example, for 1 to 5 hours under vacuum.
In addition, when the equivalent ratio R (NCO / OH) of the polyisocyanate group to the hydroxyl group is less than 1.1, the viscosity of the adhesive becomes very high, and it is difficult to apply to the base material or gel There is a case.

In this reaction, for example, known urethanization catalysts such as organic acid, tin, lead, and amine can be used as necessary.
The isocyanate group content (based on JISK1556 (2006)) of the urethane prepolymer thus obtained is, for example, 0.8 to 8.5% by weight, preferably 1.4 to 6.0% by weight. is there. Moreover, the amine equivalent (based on JISK1556 (2006)) of this urethane prepolymer is 500-5000, for example, Preferably, it is 700-3000.

The one-component curable solventless adhesive of the present invention contains titanium oxide.
The titanium oxide is not particularly limited, and examples thereof include titanium monoxide (TiO), dititanium trioxide (Ti ₂ O ₃ ), titanium dioxide (TiO ₂ ), and titanium peroxide (TiO ₃ · nH ₂ O). Can be mentioned. Preferably, titanium dioxide is used.
Examples of the titanium dioxide include crystalline titanium dioxide such as anatase type and rutile type. Preferably, rutile type titanium dioxide is mentioned from a viewpoint of improving a weather resistance in order to prevent yellowing.

Titanium dioxide is produced by a production method such as a sulfuric acid method, a chlorine method, or a gas phase method. Preferably, titanium dioxide produced by a sulfuric acid method or a chlorine method is used.
Moreover, as titanium dioxide, what is generally marketed can be used, and as such titanium dioxide, for example, Tyco R series (sulfuric acid method titanium dioxide, rutile type, manufactured by Ishihara Sangyo Co., Ltd.) is used. Specifically, R-550, R-580, R-630, R-670, R-680, R-780, R-780-2, R-820, R-830, R-850, R-855 , R-930, R-980, CR-50, CR-50-2, CR-57, CR-Super70, CR-80, CR-90, CR-90-2, CR-93, CR-95, CR -953, CR-97, UT-771, CR-60, CR-60-2, CR-63, CR-67, CR-58, CR-58-2, CR-85 and the like are used.

Moreover, the average particle diameter of titanium dioxide is 0.01-3 micrometers, for example, Preferably, it is 0.1-2 micrometers. Titanium dioxide may be treated with a treatment agent, and such a treatment agent contains atoms such as Al, Si, Zn, and the like. When titanium dioxide is treated with a treating agent, the TiO ₂ ratio is, for example, 80 to 99% by weight.

These titanium oxides can be used alone or in combination of two or more.
The blending ratio of titanium oxide is 5 to 45% by weight, preferably 10 to 42% by weight, and more preferably 20 to 40% by weight with respect to the one-component curable solventless adhesive.
If the blending ratio of titanium oxide is less than 5% by weight, chemical resistance (alkali resistance) and weather resistance after curing may be insufficient. On the other hand, if the blending ratio exceeds 45% by weight, poor dispersion of titanium oxide may occur.

  Titanium oxide is blended in the above-described blending ratio in the polyisocyanate component or polyol component before preparation of the urethane prepolymer. Moreover, it can also mix | blend with both a polyisocyanate component and a polyol component, Furthermore, it can also mix | blend with the urethane prepolymer after preparation. Preferably, it mix | blends with the polyol component before preparation of a urethane prepolymer.

  Furthermore, for one-component curable solventless adhesives, for example, antioxidants, ultraviolet absorbers, light stabilizers, fillers, and other silane coupling agents, epoxy resins, catalysts, coatings, etc., as necessary. Property improvers, leveling agents, nucleating agents, lubricants, mold release agents, antifoaming agents, plasticizers, surfactants, pigments, dyes, organic or inorganic fine particles (excluding titanium oxide), antifungal agents, flame retardants, etc. Additives can be added.

  Examples of the antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4 Phenolic antioxidants such as 8,10-tetraoxa-spiro [5,5] undecane, for example, phosphite esters such as triphenyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite Antioxidants such as phosphate ester oxidation such as dibutyl phosphate, 2-ethylhexyl acid phosphate Such as a sealing agent, and the like.

Examples of the ultraviolet absorber include triazole ultraviolet absorbers such as 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol.
Examples of the light stabilizer include hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. Examples include light stabilizers.

Examples of the filler include calcium carbonate.
As for the blending ratio of the additive, the antioxidant is, for example, 0.01 to 10% by weight, the ultraviolet absorber is, for example, 0.01 to 10%, The stabilizer is, for example, 0.01 to 10% by weight, and the filler is, for example, 0.1 to 40% by weight.
These additives can also be blended in the same manner as titanium oxide, and are preferably blended in the polyol component before preparing the urethane prepolymer.

The one-component curable solventless adhesive of the present invention thus obtained is solid at room temperature, and the viscosity (120 ° C.) is, for example, 500 to 50000 mPa · s, preferably 800 to 30000 mPa · s. It is. The viscosity can be measured with a cone plate viscometer (conforming to JISK5600-2-3 (1999)).
The residual amount of the polyisocyanate monomer in the one-component curable solventless adhesive of the present invention is, for example, less than 1% by weight, preferably less than 0.8% by weight, and more preferably less than 0.5% by weight. It is.

When the residual amount of the polyisocyanate monomer is 1% by weight or more, the odor of the polyisocyanate monomer becomes tight when the adhesive is heated and applied, which may hinder workability.
In the one-component curable solventless adhesive of the present invention, in order to make the remaining amount of the polyisocyanate monomer less than 1% by weight, for example, a polyisocyanate monomer derivative in which the remaining amount of the polyisocyanate monomer is less than 1% by weight. Only the polyisocyanate component is used to react it with the polyol component. Alternatively, a polyisocyanate monomer is first used as a polyisocyanate component, which is reacted with a polyol component so that the equivalent ratio R (NCO / OH) of isocyanate groups to hydroxyl groups is 1 or less, and then polyisocyanate. A monomer derivative is used as a polyisocyanate component and is reacted so that the equivalent ratio R (NCO / OH) of all isocyanate groups to hydroxyl groups is 1 or more. Furthermore, the remaining amount of the polyisocyanate monomer is 1% by weight or more, and the remaining amount of the polyisocyanate monomer of the urethane prepolymer having an isocyanate group at the molecular end is reduced to less than 1% by weight by a known thin film distillation method or the like. Decrease. In addition, the residual amount of the polyisocyanate monomer in the one-component curable solventless adhesive of the present invention can be measured by, for example, HPLC measurement.

The one-component curable solventless adhesive of the present invention can be used, for example, for bonding various industrial products such as paper, natural or artificial leather, film, and fiber material, and preferably a paste containing at least a fiber material. Used for bonding (bonding) together products.
In addition, the one-component curable solventless adhesive is specifically used for adhesion between fiber materials and adhesion between fiber materials and paper, natural or artificial leather, and films.

Examples of the fiber material include woven fabrics such as silk, linen, cotton, rayon woven fabric, and polyester woven fabric, and non-woven fabrics such as vinylon nonwoven fabric and polyester nonwoven fabric.
Examples of the film include films formed from polymers such as urethane polymers, olefin polymers, and vinyl polymers.
Moreover, in order to adhere fiber materials using a one-component curable solventless adhesive, for example, gravure coater, doctor coater, bar coater, roll coater, reverse roll coater, curtain coater, spray coater, curtain spray coater, A one-component curable solventless adhesive is applied to a fiber material by a coating method such as a bead, spiral, or slot, cooled, remelted, and bonded together.

  Specifically, for example, a one-component curable non-solvent adhesive heated and melted at 50 to 150 ° C. is applied to an adherend (for example, film, fiber, etc.) to form an adhesive layer. Then, it bonds together before cooling solidification, or it cools, Then, it reheats to 50-150 degreeC, an adhesive bond layer is remelted, and another to-be-adhered body is bonded together. Or it cools after application | coating, another adherend is bonded together, it heats again and it bonds. Thereafter, the adhesive layer is moisture-cured for 1 to 14 days, for example, to obtain a laminate of fiber materials.

  In the bonding, a release paper can be used. For example, a one-component curable non-solvent adhesive heated and melted at 50 to 150 ° C. is applied to the release paper to form an adhesive layer. Thereafter, the fiber material is bonded to the adhesive layer on the release paper, cooled, and then the release paper is peeled from the adhesive layer. Then, it reheats to 50-150 degreeC, an adhesive bond layer is remelted, and a fiber raw material is bonded together. Thereafter, the adhesive layer is moisture-cured.

According to the one-component curable solventless adhesive of the present invention, the yellowing of the fiber material laminate over time can be suppressed, and the alkali resistance can be improved. It is possible to suppress deformation and a decrease in adhesive strength.
Therefore, the one-component curable solventless adhesive of the present invention can be used as, for example, a reactive hot-melt adhesive for bonding fiber materials, for example, for bonding white or light-colored fiber materials. Specifically, for example, it can be used for bonding fiber materials in the production of care sheets and the like.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
Example 1
In a separable flask equipped with a temperature controller and a stirrer, 120 parts by weight of polyester polyol (1), 112.68 parts by weight of polyester polyol (2), 152 parts by weight of polypropylene glycol (1), 400 parts by weight of titanium oxide (1) , 1.8 parts by weight of the antioxidant (1), 0.6 parts by weight of the ultraviolet absorber (1), and 1.8 parts by weight of the light stabilizer (1), and vacuum while stirring at 100 to 110 ° C. for 5 hours Dehydrated. Subsequently, 0.3 weight part of antioxidant (2) was added, and vacuum dehydration was performed with stirring at 95 to 105 ° C. for 30 minutes.

Thereafter, 83.9 parts by weight of polyisocyanate (2) and 126 parts by weight of polyisocyanate (3) were added and reacted at 90 to 100 ° C. for 2 hours under vacuum to produce a reactive hot melt adhesive (isocyanate group content: 2.0 wt%, HDI residual amount: 0.1 wt%, viscosity: 3600 mPa · s (120 ° C)).
Examples 2 to 5, Reference Example 6 and Comparative Examples 1 to 5
Reactive hot melt adhesives of Examples 2 to 5, Reference Example 6 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1 except that the reaction was carried out according to the formulation shown in Table 1. In Reference Example 6 , separation of residual HDI was observed during remelting. Moreover, about the comparative example 1, the titanium oxide was not disperse | distributed uniformly.

Table 1 shows the formulation of Examples 2 to 5, Reference Example 6 and Comparative Examples 1 to 5.

Details of the abbreviations in Table 1 are shown below.
Polyisocyanate (1): Diphenylmethane diisocyanate (MDI), Millionate MT-F, manufactured by Nippon Polyurethane Co., Ltd. Polyisocyanate (2): Takenate D-177N, isocyanurate / allophanate derivative of hexamethylene diisocyanate (HDI), manufactured by Mitsui Chemicals Polyurethanes Polyisocyanate (3): Takenate D-178N, hexamethylene diisocyanate (HDI) allophanate derivative, Mitsui Chemicals Polyurethane Polyisocyanate (4): Hexamethylene diisocyanate (HDI), Mitsui Chemicals Polyurethane Polyester polyol (1): Isophthalic acid / phthalic acid / adipic acid / ethylene glycol / neopentyl glycol, number average molecular weight 3,500, polyester polyol manufactured by Toyokuni Oil Co., Ltd. (2): Phthalic acid / adipic acid / ethylene glycol / neopentyl glycol, number average molecular weight 2000, manufactured by Ube Industries, Ltd. Polypropylene glycol (1): Actol P-22, number average molecular weight 1000, titanium oxide manufactured by Mitsui Chemicals Polyurethanes (1): Typeke R-820, average particle size 0.26 μm, TiO ₂ ratio 93% by weight, treated product treated with a treating agent containing Al, Si, Zn, antioxidant manufactured by Ishihara Sangyo Co., Ltd. (1) : 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10- Tetraoxa-spiro [5,5] undecane, manufactured by Sumitomo Chemical Co., Ltd. Antioxidant (2): Tris (tridecyl) phosphite, manufactured by Johoku Chemical Co., Ltd. Light stabilizer (1): Bi (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by Sankaiki Chemical Co., Ltd. UV absorber (1): 2- (2H-benzotriazol-2-yl) -4- (1, 1,3,3-tetramethylbutyl) phenol, manufactured by Ciba Specialty Chemicals, Inc. (1): NS200, calcium carbonate, manufactured by Nitto Flour Industry Co., Ltd. In Table 1, the final amine equivalent is JISK1556 (2006). Measured in conformity. Moreover, the residual amount of the polyisocyanate monomer was measured by HPLC.

Evaluation 1) Viscosity measurement The viscosity at 100 ° C. and 120 ° C. of the reactive hot melt adhesives of Examples 2 to 5, Reference Example 6 and Comparative Examples 2 to 5 was measured using a cone plate viscometer (JIS K5600-2-3 ( 1999)). The results are shown in Table 1.
2) Production of cured film The reactive hot melt adhesives of Examples 2 to 5, Reference Example 6 and Comparative Examples 2 to 5 previously heated to 120 ° C. were dropped on the release paper, and the film thickness became about 100 microns. Thus, a film was prepared with a doctor blade, and after that, the film was left to stand for 5 days under conditions of 30 ° C. and 60% RH to cure the film, thereby obtaining a cured film.
3) Production of bonded product The one-component curable solventless adhesives of Examples 2 to 5, Reference Example 6 and Comparative Examples 2 to 5 previously heated to 120 ° C. were dropped on the release paper to bond the bonded products. An adhesive layer was formed with a doctor blade so that the thickness of the agent layer was about 100 microns, and a commercial mattress sheet (65% polyester, 35% cotton) was immediately bonded.

Next, this was stored in a refrigerator for 3 minutes, and after removal, the release paper was peeled from the adhesive layer and heated in an oven at 120 ° C. for 90 seconds. After heating, the sheet was taken out of the oven and immediately, the mattress sheet was further bonded to the adhesive layer and left to stand for 5 days under conditions of 30 ° C. and 60% RH to cure the moisture.
4) Odor during heating The odor when the adhesive was heated was evaluated during the above operations 1) to 3). The results are shown in Table 1.

○: No odor during heating.
Δ: Odor when heated.
×: Very odor when heated.
5) Weather resistance test The cured film obtained by the preparation of the above 2) cured film was set in a UV auto fade meter U48AU type tester (manufactured by Suga Test Instruments Co., Ltd.), and under conditions of 63 ° C. and 50% RH. The sample was irradiated with ultraviolet rays for 24 hours.
6) Immersion test of cured film 2) The cured film obtained by the preparation of the cured film is obtained by using a sodium hypochlorite solution (effective chlorine 5.0% or more, alkaline, manufactured by Wako Pure Chemical Industries, Ltd.) in distilled water. The sample was soaked in a solution diluted 50 times with the solution and stored at 50 ° C for 24 hours. Thereafter, the cured film was taken out, rinsed thoroughly with running water, then wiped with a waste cloth, and dried at 50 ° C. for 24 hours.
7) Immersion test of bonded product The above 3) bonded product obtained by preparing the bonded product is a sodium hypochlorite solution (available chlorine 5.0% or more, alkaline, manufactured by Wako Pure Chemical Industries, Ltd.) Was immersed in a solution diluted 50 times with distilled water and stored at 80 ° C. for 24 hours. Thereafter, the bonded product was taken out, rinsed thoroughly with running water, then wiped with a waste cloth, and dried for 3 to 4 hours with an air blow dryer at 80 ° C.
8) Evaluation of degree of yellowing The b value of the cured film before and after UV irradiation in the above 5) weather resistance test was measured with a spectroscopic colorimeter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The difference (Δb) in the b value before and after irradiation was calculated to evaluate the degree of yellowing of the cured one-part curable solventless adhesive. Δb represents the degree of yellowing. The results are shown in Table 1. Note that the value of Δb in the test is preferably 1 or less.

The degree of yellowing was also evaluated in the same manner for the above 6) cured film before and after immersion in the cured film immersion test, and 7) the bonded product before and after immersion in the bonded article immersion test. The results are shown in Table 1. In addition, the value of Δb in the immersion test of the cured film 6 is preferably 1 or less, and the value of Δb in the immersion test of the bonded product 7 is preferably 8 or less. .
9) Measurement of adhesive strength 7) Measure the adhesive strength of the bonded product before and after immersion in the bonded product immersion test using a precision universal material testing machine 201B type (manufactured by Intesco). The measurement was performed at 25 mm and a tensile speed of 100 mm / min. The results are shown in Table 1.

Claims (4)

A one-component curable solventless adhesive obtained by reacting a polyisocyanate component and a polyol component,
The polyisocyanate component includes a derivative of an aliphatic polyisocyanate and / or a derivative of an araliphatic polyisocyanate,
Contains titanium oxide ,
A one-component curable solventless adhesive , wherein the content of titanium oxide is 5 to 45% by weight . Induced conductors, characterized in that allophanate derivatives and / or isocyanurate derivatives, one-part curing type non solvent adhesive according to claim 1. The one-component curable solventless adhesive according to claim 1 or 2 , wherein the residual amount of the polyisocyanate monomer is less than 1% by weight. The one-component curable solventless adhesive according to any one of claims 1 to 3 , which is used for adhering at least fibers.