JP7339505B2 - Polyurethane adhesive composition - Google Patents

Description

The present invention relates to polyurethane adhesive compositions.

In recent years, there is a system that uses IoT (Internet of Things) to monitor information (eg, air pressure, wear, etc.) of tires mounted on automobiles.

In the above system, in order to monitor the information of the tire as described above, the tire usually has an electronic device or a case for accommodating the electronic device (hereinafter referred to as "electronic device etc.") inside or outside the tire. However, in that case, it is necessary to fix the electronic device and the like to the tire with, for example, an adhesive layer.

Conventionally, there is a method of vulcanizing an adhesive layer together with an unvulcanized tire in advance, for example, in order to fix the electronic device or the like to a tire (for example, Patent Document 1).
WO 2005/010002 relates to a tire ready to receive elements, e.g. electronic elements, fixed to the inner and/or outer surface of the tire, comprising a receiving area, an adhesive layer arranged on said receiving area, and said adhesive A tire comprising an inner surface and/or an outer surface having a protective film disposed thereon, wherein the composition of said adhesive layer has a molar content of diene units greater than 10% relative to all elastomer block units Tires and the like are described which are based on a block thermoplastic elastomer (TPE) comprising a diene elastomer block having a
In Patent Document 1, the adhesive layer is vulcanized with the unvulcanized tire blank ([0101]-[0105], etc.).

Japanese Patent Publication No. 2018-501366

However, as described above, when an adhesive layer is partially arranged in an unvulcanized tire (or tire blank) and vulcanized, the positions where electronic devices and the like are attached can be freely determined in the tire after vulcanization. Since it cannot be set, it was considered to lack versatility.
In addition, it has been considered that placing the adhesive over a wide portion or the entirety of the inside or outside of the tire in order to freely set the mounting position of the electronic device or the like on the tire lacks productivity.
Therefore, an object of the present invention is to provide an adhesive composition that can be applied to vulcanized rubber to bond the vulcanized rubber.

As a result of intensive research to solve the above problems, the present inventors have found a urethane compound containing a polyisocyanate compound and ricinoleic acid glyceride, wherein the ricinoleic acid-derived double bond in the ricinoleic acid glyceride may be modified. The present inventors have found that the vulcanized rubber can be adhered by applying the adhesive composition to the vulcanized rubber, leading to the present invention.
The present invention is based on the above knowledge and the like, and specifically solves the above problems with the following configuration.

[1] a polyisocyanate compound;
ricinoleic acid glyceride, wherein the double bond derived from ricinoleic acid in the ricinoleic acid glyceride may be modified,
A polyurethane adhesive composition applied to vulcanized rubber.
[2] The polyurethane-based adhesive composition according to [1], wherein the double bond derived from ricinoleic acid in the ricinoleic acid glyceride is modified.
[3] The polyurethane-based adhesive composition according to [1] or [2], wherein the ricinoleic acid glyceride has a melting point of 35°C or lower.
[4] The polyurethane adhesive composition according to any one of [1] to [3], wherein the polyisocyanate compound is liquid at room temperature.
[5] Any one of [1] to [4], wherein the molar ratio (NCO/OH) of the isocyanate groups of the polyisocyanate compound to the hydroxyl groups of the ricinoleic acid glyceride is 0.3 to 1.8. The polyurethane-based adhesive composition described.
[6] The polyurethane-based adhesive composition according to any one of [1] to [5], which further contains a filler.
[7] The polyurethane-based adhesive composition according to [6], wherein the filler is clay.
[8] The polyurethane adhesive composition according to [6] or [7], wherein the content of the filler is 10 to 70% by mass relative to the total amount of the polyurethane adhesive composition.
[9] The polyurethane adhesive composition according to any one of [1] to [8], which further contains a plasticizer.
[10] The polyurethane adhesive composition according to [9], wherein the plasticizer has an SP value of 20 (MPa) ^1/2 or more.
[11] The polyurethane adhesive composition according to [9] or [10], wherein the plasticizer has a molecular weight of 1,000 or less.
[12] The polyurethane adhesive composition according to any one of [9] to [11], wherein the content of the plasticizer is 1 to 20% by mass with respect to the total amount of the polyurethane adhesive composition. .
[13] The polyurethane-based adhesive composition according to any one of [1] to [12], wherein the ricinoleic acid glyceride has a substituent due to modification of the double bond derived from ricinoleic acid in the ricinoleic acid glyceride. thing.

The urethane-based adhesive composition of the present invention can be applied to vulcanized rubber to bond the vulcanized rubber.

The present invention will be described in detail below.
In this specification, the numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
In this specification, unless otherwise specified, each component can be used singly or in combination of two or more substances corresponding to the component. When the component contains two or more substances, the content of the component means the total content of the two or more substances.

[Urethane adhesive composition]
The urethane-based adhesive composition of the present invention (the composition of the present invention) is
a polyisocyanate compound;
ricinoleic acid glyceride, wherein the double bond derived from ricinoleic acid in the ricinoleic acid glyceride may be modified,
It is a polyurethane-based adhesive composition that is applied to vulcanized rubber.

Since the composition of the present invention has such a constitution, it is believed that the desired effect can be obtained. Although the reason is not clear, it is presumed to be approximately as follows.
The ricinoleic acid glyceride contained in the composition of the present invention has hydroxyl groups derived from ricinoleic acid.
Therefore, the ricinoleic acid glyceride reacts with the polyisocyanate compound contained in the composition of the present invention, and can become a polyurethane-based adhesive after the reaction.

Here, in the ricinoleic acid glyceride, if all or part of the ricinoleic acid-derived double bonds are not modified, the ricinoleic acid-derived double bonds are introduced into the polyurethane-based adhesive. The composition is believed to have a high affinity with vulcanized rubber.
In addition, in the ricinoleic acid glyceride, when all or part of the double bonds derived from ricinoleic acid are modified and the ricinoleic acid glyceride has a substituent due to the modification, the substituent is introduced into the polyurethane adhesive, It is believed that the above substituents react or interact in some way with vulcanized rubber (collectively referred to as "reactive").
As described above, the composition of the present invention has affinity and/or reactivity with vulcanized rubber due to the double bonds and/or substituents derived from ricinoleic acid glyceride, thereby is applied to vulcanized rubber, the composition of the present invention (or the polyurethane-based adhesive obtained from the composition of the present invention) can adhere vulcanized rubber. Infer.
Each component contained in the composition of the present invention will be described in detail below.

<Polyisocyanate compound>
The polyisocyanate compound contained in the composition of the present invention is not particularly limited as long as it has two or more isocyanate groups in its molecule.
Examples of polyisocyanate compounds include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate ( TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalenediisocyanate (NDI), aromatic polyisocyanate compounds such as triphenylmethane triisocyanate;
Hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (H ₆ XDI) aliphatic (where aliphatic is a concept including linear, branched and cycloaliphatic) polyisocyanates such as , dicyclohexylmethane diisocyanate (H ₁₂ MDI);
These carbodiimide-modified polyisocyanates are included.

Among these, the polyisocyanate compound is preferably an aromatic polyisocyanate, more preferably MDI and/or polymeric MDI, because of its excellent adhesiveness to vulcanized rubber and excellent curability.
Polymeric MDI is polymethylene polyphenyl polyisocyanate. Polymeric MDI may be a mixture of polymethylene polyphenyl polyisocyanates with different degrees of polymerization.
Polymeric MDI may contain MDI in addition to polymethylene polyphenyl polyisocyanate.

The polyisocyanate compound is preferably liquefied at room temperature (23° C.) from the standpoint of better adhesion to vulcanized rubber.
Examples of polyisocyanate compounds that are liquid at room temperature include polymeric MDI.

<Ricinoleic acid glyceride>
Ricinoleic acid glycerides (ricinoleic acid glycerides) contained in the composition of the present invention are esters of ricinoleic acid and glycerin. The ricinoleic acid glycerides may be derived, for example, from castor oil-based polyols. Castor oil-based polyols are generally glycerides composed of fatty acids (including unsaturated fatty acids and saturated fatty acids whose main component is ricinoleic acid), and have a plurality of hydroxy groups.
In the present invention, the ricinoleic acid-derived double bond in the ricinoleic acid glyceride may be modified. In the present invention, as the ricinoleic acid glyceride modified as described above, for example, a castor oil-based polyol having a modified double bond can be used.
Hereinafter, the ricinoleic acid glyceride contained in the composition of the present invention (including the case where the ricinoleic acid-derived double bond in the ricinoleic acid glyceride is modified) may be referred to as "ricinoleic acid glyceride". .

Ricinoleic acid that can constitute the ricinoleic acid glyceride is a compound represented by the following structural formula. Ricinoleic acid has a double bond in the molecule as described below.

Examples of the ricinoleic acid glyceride include ricinoleic acid monoglyceride (compound in which one of the three hydroxyl groups of glycerin forms an ester bond with ricinoleic acid), ricinoleic acid diglyceride (two of the three hydroxyl groups of glycerin are ricinoleic acid). compound that forms an ester bond with) and ricinoleic acid triglyceride (a compound in which all three hydroxyl groups of glycerin form an ester bond with ricinoleic acid), or a mixture containing at least two . In the above, the double bond derived from ricinoleic acid may or may not be modified.
When the ricinoleic acid glyceride is ricinoleic acid mono- or diglyceride, a fatty acid other than ricinoleic acid may be ester-bonded to the hydroxy group of the glycerin residue. Hydroxy groups of the above residues may be present as is.

The ricinoleic acid glyceride (ricinoleic acid mono-, di-, or triglyceride) preferably contains a polyol having a total of at least three hydroxyl groups derived from ricinoleic acid and glycerol per molecule.
The ricinoleic acid glyceride preferably has a total of three hydroxyl groups per molecule.

When the ricinoleic acid glyceride (including the case where it is modified) is derived from a castor oil-based polyol (including the case where the castor oil-based polyol is modified), the castor oil-based polyol containing the ricinoleic acid glyceride is It is preferable to have an average of 2.5 or more hydroxyl groups per molecule. In addition, the hydroxyl group does not include a functional group (for example, OH in the carboxy group) resulting from the modification.

The ricinoleic acid glyceride preferably contains ricinoleic acid triglyceride from the viewpoint of superior adhesion to vulcanized rubber.
In the ricinoleic acid triglyceride, the double bond derived from ricinoleic acid may or may not be modified. At least a portion is preferably modified.

When the ricinoleic acid glyceride contains ricinoleic acid triglyceride, the ricinoleic acid glyceride can further contain ricinoleic acid monoglyceride and/or ricinoleic acid diglyceride in addition to ricinoleic acid triglyceride. In the above case, at least part of the ricinoleic acid-derived double bonds in the ricinoleic acid diglyceride may be modified. The double bond derived from ricinoleic acid in the ricinoleic acid monoglyceride may be modified.

Non-denatured ricinoleic acid triglyceride can be represented, for example, by the following formula (1).

In the ricinoleic acid triglyceride represented by the above formula (1), when the double bond derived from ricinoleic acid is modified, which double bond is modified is not particularly limited.

(denaturation)
In the present invention, the ricinoleic acid-derived double bond in the ricinoleic acid glyceride may be modified.

As described above, in the present invention, the ricinoleic acid glyceride modified as described above includes, for example, double bonds possessed by castor oil-based polyols (specifically, unsaturated fatty acids constituting castor oil-based polyols (for example, containing ricinoleic acid, and may also contain oleic acid and linoleic acid.)) modified (modified castor oil-based polyol) can be used.
Modified castor oil-based polyols can include ricinoleic acid glycerides in which double bonds derived from ricinoleic acid have been modified as described above. That is, when the composition of the present invention contains modified ricinoleic acid glycerides, the composition of the present invention can contain modified castor oil-based polyols as modified ricinoleic acid glycerides. (same below)

From the viewpoint that the double bond derived from ricinoleic acid in the ricinoleic acid glyceride (or the double bond derived from the unsaturated fatty acid constituting the castor oil-based polyol; hereinafter the same) is superior in adhesion to vulcanized rubber, It is preferably denatured.
Ricinoleic acid glycerides in which double bonds derived from ricinoleic acid are modified are hereinafter sometimes referred to as "modified ricinoleic acid glycerides".

When the double bonds derived from ricinoleic acid in the ricinoleic acid glyceride are modified, all or part of the double bonds may be modified.
In the ricinoleic acid glyceride, at least a portion of the double bonds are preferably modified, and more preferably all of the double bonds are modified, from the viewpoint of better adhesion to vulcanized rubber. preferable.

When the ricinoleic acid-derived double bond in the ricinoleic acid glyceride is modified, the modified ricinoleic acid glyceride can have a substituent due to the modification.
Examples of the substituents include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof;
Functional groups such as carboxy groups are included.
The above substituent and the ricinoleic acid skeleton in the modified ricinoleic acid glyceride can be bonded directly or via a divalent linking group. The linking group is not particularly limited.

The substituent is preferably a polar group, more preferably an acid group, still more preferably a carboxy group, from the viewpoint of better adhesion to the vulcanized rubber, and all of the double bonds are carboxy groups. It is particularly preferred that it is modified with

From the viewpoint that the ricinoleic acid glyceride has excellent adhesion to vulcanized rubber,
It preferably contains ricinoleic acid triglyceride in which the double bond derived from ricinoleic acid may be modified,
More preferably, it contains a modified ricinoleic acid triglyceride in which the double bond derived from ricinoleic acid is modified,
It further preferably contains carboxy-modified ricinoleic acid triglyceride in which the double bond derived from ricinoleic acid is modified with a carboxy group,
It is particularly preferred to include all carboxy-modified ricinoleic acid triglycerides in which all double bonds derived from ricinoleic acid are modified with carboxy groups.

When the ricinoleic acid glyceride contains modified ricinoleic acid triglyceride, the ricinoleic acid glyceride is at least one selected from the group consisting of non-modified ricinoleic acid triglyceride, ricinoleic acid monoglyceride and ricinoleic acid diglyceride in addition to modified ricinoleic acid triglyceride. May contain seeds. In the above case, at least part of the ricinoleic acid-derived double bonds in the ricinoleic acid diglyceride may be modified. In the above ricinoleic acid monoglyceride, the double bond derived from ricinoleic acid may be modified.

(melting point of ricinoleic acid glyceride)
The melting point of the ricinoleic acid glyceride is preferably +35° C. or lower, more preferably −50° C. to 0° C., from the viewpoint of better adhesion to vulcanized rubber.
In the present invention, the exothermic peak temperature of ricinoleic acid glyceride measured using a DSC (differential scanning calorimeter) can be taken as the melting point of ricinoleic acid glyceride.

A commercial item can be used as the ricinoleic acid glyceride.
Examples of the commercially available product include URIC H-30 manufactured by Ito Oil Co., Ltd., and the like.

(NCO/OH)
Molar ratio of the isocyanate groups of the polyisocyanate compound to the hydroxyl groups of the ricinoleic acid glyceride (including the case where it is modified) or the castor oil-based polyol containing the ricinoleic acid glyceride (including the case where it is modified). (NCO/OH, also referred to as index) is preferably 0.3 to 1.8, more preferably 0.9 to 1.3, from the viewpoint of better adhesion to vulcanized rubber. preferable. In addition, the hydroxyl group does not include a functional group (for example, OH in the carboxy group) resulting from the modification.

(Content of ricinoleic acid glyceride)
The content of the cinoleic acid glyceride (including the case where it is modified) is 5 to 50 parts by mass with respect to 10 parts by mass of the polyisocyanate compound from the viewpoint of better adhesion to the vulcanized rubber. It is preferably 7 to 20 parts by mass, even more preferably 8 to 15 parts by mass, and even more preferably 8 to 12 parts by mass.

(filler)
The composition of the invention can further contain fillers.
It is preferable that the composition of the present invention further contains a filler from the standpoint of better adhesion to vulcanized rubber.

Examples of the filler include clay, silica, and calcium carbonate.
The filler may be surface-treated. The surface treatment agent used for surface treatment is not particularly limited. Examples include fatty acids, resin acids, urethane compounds, and fatty acid esters.

Clay is preferable as the filler from the viewpoint of excellent adhesion to the vulcanized rubber.
Examples of the clay include bentonite.
Naturally occurring bentonites usually contain impurities such as quartz and feldspar in addition to clay minerals (eg, montmorillonite).
Purified bentonite is preferable as the bentonite from the viewpoint of superior adhesion to vulcanized rubber.
Purified bentonite means bentonite in which the purity of montmorillonite, which is the main component, is higher than that of naturally occurring bentonite.

(filler content)
The content of the filler is preferably 10 to 70% by mass with respect to the total amount of the composition of the present invention (the polyurethane adhesive composition) from the viewpoint of better adhesion to vulcanized rubber. 20 to 60% by mass is more preferable, and 20 to 50% by mass is even more preferable.

(plasticizer)
It is preferable that the composition of the present invention further contain a plasticizer from the standpoint of better adhesion to vulcanized rubber.

Examples of the plasticizer include ester compounds such as diisononyl phthalate (DINP), dioctyl adipate, isodecyl succinate, diethylene glycol dibenzoate, and butyl oleate;
aroma oil;
Examples thereof include compound A represented by the following formula (1).

In formula (1), R ¹ is an amino group (—NH ₂ ), a hydrogen atom, or a hydrocarbon group, R ² and R ³ are each independently a hydrocarbon group optionally having a heteroatom, Alternatively, it is a hydrogen atom.

The plasticizer is preferably the compound A represented by the above formula (1) from the viewpoint of superior adhesion to the vulcanized rubber.
The inventors presume that this is because the compound A represented by the formula (1) as a plasticizer can permeate the vulcanized rubber.
Therefore, when the composition of the present invention further contains the compound A and is applied to vulcanized rubber, the compound A permeates the vulcanized rubber, and along with the permeation of the compound A, the polyisocyanate and The present inventor believes that the ricinoleic acid glyceride also penetrates into the vulcanized rubber, and that the anchoring effect of the polyisocyanate and/or the ricinoleic acid glyceride is obtained.

(Compound A)
The compound A is a compound represented by the following formula (1).

In formula (1), R ¹ is an amino group (—NH ₂ ), a hydrogen atom, or a hydrocarbon group, R ² and R ³ are each independently a hydrocarbon group optionally having a heteroatom, Alternatively, it is a hydrogen atom.

In the above formula (1), the hydrocarbon group as R ¹ is not particularly limited. Examples of hydrocarbon groups include aliphatic hydrocarbon groups (including linear, branched, and cyclic), aromatic hydrocarbon groups, and combinations thereof. The hydrocarbon group may have an unsaturated bond.
The number of carbon atoms in the hydrocarbon group is preferably 20 or less, more preferably 1-15.
Examples of hydrocarbon groups include aliphatic hydrocarbon groups such as methyl, ethyl, butyl, pentyl, hexyl, octyl, decyl and dodecyl groups.

In the above formula (1), the heteroatom is not particularly limited. Heteroatoms include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, halogens, and the like. A heteroatom may be combined with another heteroatom, carbon atom or hydrogen atom to form a functional group.
When R ¹ is an amino group, R ² and R ³ are preferably each independently a hydrocarbon group or a hydrogen atom.
When R ¹ is a hydrogen atom, R ² and R ³ are each independently a hydrocarbon group, or R ² is a hydrocarbon group and R ³ is a hydrogen atom.

Compound A includes, for example, compounds in which R ¹ is an amino group; compounds in which R ¹ is a hydrogen atom; and compounds in which R ¹ is a hydrocarbon group.
Compounds in which R ¹ is an amino group include, for example, urea (NH ₂ CONH ₂ ).
Compounds in which R ¹ is a hydrogen atom include, for example, N,N-dimethylformamide and N-methyl-N-isopropylformamide.
Compounds in which R ¹ is a hydrocarbon group include, for example, N,N-dimethylacetamide and N-methyl-N-isopropylacetamide.

The compound A is preferably a compound in which R ¹ is an amino group, a compound in which R ¹ is a hydrogen atom, and urea, N,N-dimethyl Formamide is more preferred.

(SP value of plasticizer)
The SP value of the plasticizer is preferably 20 (MPa) ^1/2 or more from the viewpoint of excellent adhesion to vulcanized rubber and high anchoring effect.
The upper limit of the SP value is not particularly limited. For example, it can be 30 (MPa) ^1/2 or less.

In the present invention, the SP value (solubility parameter) was calculated by applying the molecular volume and molecular cohesive energy values in the literature Properties of Polymers 3rd Edition Part 3 and Part 4 to the chemical structures of polyurethane and epoxy resins.

Plasticizers having an SP value of 20 (MPa) ^1/2 or more include, for example, urea and N,N-dimethylformamide.

(Molecular weight of plasticizer)
The molecular weight of the plasticizer is preferably 1,000 or less, more preferably 50 to 200, and even more preferably 60 to 100, from the viewpoints of excellent adhesion to vulcanized rubber and high anchoring effect.

The molecular weight of the plasticizer can be measured, for example, by a conventionally known method.
When the plasticizer is a low-molecular-weight compound (not a polymer), the molecular weight of the plasticizer may be measured, for example, by a conventionally known method.

(Plasticizer content)
The content of the plasticizer is preferably 1 to 20% by mass with respect to the total amount of the composition of the present invention (the polyurethane adhesive composition) from the viewpoint of better adhesion to vulcanized rubber. , 1 to 10 mass % is more preferred.

The compositions of the present invention can be one-part or two-part.
(Two-component adhesive composition)
When the composition of the present invention is of a two-component type, the two-component adhesive composition can have a main agent and a curing agent (curing agent in a broad sense).
- Main agent The above-mentioned main agent should just contain the above-mentioned polyisocyanate compound at least. The main agent may be only the polyisocyanate compound.

Curing agent The (broadly defined) curing agent may contain a compound (narrowly defined curing agent) having a plurality of active hydrogen-containing groups in one molecule. The narrowly defined curing agent means a compound that substantially reacts with the polyisocyanate compound to cure the adhesive composition. The curing agent in the broad sense should include at least the curing agent in the narrow sense.
Examples of the curing agent in the narrow sense include the above ricinoleic acid glycerides.

(other optional ingredients)
The composition of the present invention may optionally contain a polyol other than the ricinoleic acid glyceride, a curing catalyst, an anti-aging agent, an antioxidant, a silane coupling agent, a pigment (dye), as long as the object of the present invention is not impaired. Various additives such as tackifiers, thixotropic agents, UV absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, and antistatic agents may be further included.
Moreover, when the composition of the present invention is of a two-pack type, it can be appropriately selected whether the optional component is added to the main agent or the curing agent.
In addition, polyols other than the above-mentioned ricinoleic acid glyceride are mentioned as one of preferred aspects to be added to the curing agent.

Curing catalyst The curing catalyst is not particularly limited, but specific examples include carboxylic acids such as 2-ethylhexanoic acid and oleic acid; phosphoric acids such as polyphosphoric acid, ethyl acid phosphate and butyl acid phosphate; and bismuth octylate. bismuth catalysts such as; dibutyltin dilaurate, dioctyltin dilaurate and other tin-based catalysts; ), tertiary amine catalysts such as compounds containing a dimorpholinodiethyl ether structure, and the like.
The curing catalyst is preferably a tin-based catalyst.
The amount of curing catalyst can be selected as appropriate.

(Production method)
When the composition of the present invention is a one-liquid type, its production method is not particularly limited. be able to.

When the composition of the present invention is a two-component composition, the production method is not particularly limited. For example, the main component and the curing agent are placed in separate containers, and mixed in each container under a nitrogen gas atmosphere. It can be manufactured by a method.
Moreover, as a method of using a two-liquid type, the main agent and the curing agent may be mixed and used.

<Applied to vulcanized rubber>
The compositions of the invention are applied to vulcanizates.
The vulcanized rubber to which the composition of the present invention is applied is not particularly limited as long as it is vulcanized rubber (rubber after vulcanization).
The vulcanization is preferably sulfur vulcanization.
Examples of the vulcanized rubber include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), aromatic vinyl-conjugated diene copolymer rubber (eg, styrene-butadiene rubber), acrylonitrile-butadiene copolymer rubber. (NBR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR), vulcanized diene rubber such as chloroprene rubber (CR).

The vulcanized rubber preferably contains a halogenated butyl rubber from the viewpoint of excellent adhesion to the composition of the present invention.
The vulcanized rubber may further contain a non-diene rubber and a thermoplastic resin in addition to the diene rubber.

In addition to the rubber component, the vulcanized rubber further contains a filler such as carbon black or silica, a silane coupling agent, zinc oxide, stearic acid, an anti-aging agent, a processing aid, an oil (for example, a process Various additives commonly used in rubber compositions such as oils, aromatic oils), liquid polymers, vulcanizing agents (eg, sulfur), and vulcanization accelerators can be included.

Examples of the vulcanized rubber include diene-based rubbers, non-diene-based rubbers that can be used as necessary, thermoplastic resins, and vulcanized rubber compositions containing the various additives described above.
The vulcanization conditions are not particularly limited.

As a method of using the composition of the present invention, for example, first, the composition of the present invention is applied to vulcanized rubber (application step).
The method of applying the composition of the present invention to vulcanized rubber is not particularly limited.
When the composition of the present invention is applied to vulcanized rubber, the thickness can be, for example, 0.5 to 2.0 mm.

(vulcanized rubber)
The composition of the present invention is capable of bonding vulcanized rubber as described above.
In addition, the composition of the present invention can adhere vulcanized rubbers together.
At this time, the types of vulcanized rubber may be the same or different.
When the composition of the present invention is used to bond vulcanized rubbers together, the composition of the present invention can be applied to one vulcanized rubber or both vulcanized rubbers.

Examples of the vulcanized rubber as a member include vulcanized rubber forming the inner or outer surface of a tire, and vulcanized rubber as a case for housing an electronic device.
When vulcanized rubber is used as the case, the case may cover the whole or part of the electronic device, for example.
The electronic device housed in the case is not particularly limited.

Using the composition of the present invention, for example, when bonding vulcanized rubber X constituting the inside or outside of a tire and vulcanized rubber Y containing electronic equipment, first, one vulcanized rubber or both vulcanized rubbers The composition of the present invention may be applied to sulfur rubber.
Next, the vulcanized rubber X and the vulcanized rubber Y may be arranged so that the composition of the present invention is interposed therebetween.

Curing step Next, the vulcanized rubber to which the composition of the present invention is applied is cured under conditions of, for example, 10 to 80 ° C. and 20 to 80% relative humidity (% RH) to obtain the A laminate having an adhesive layer (polyurethane-based adhesive) made of the composition can be obtained.
In addition, when a plurality of vulcanized rubbers are arranged through the composition of the present invention, the plurality of vulcanized rubbers arranged through the composition of the present invention, for example, under the same conditions as above By placing and curing, a laminate having an adhesive layer (polyurethane-based adhesive) made of the composition of the present invention interposed therebetween can be obtained.

EXAMPLES The present invention will be specifically described below with reference to Examples. However, the present invention is not limited to these.

<Production of adhesive composition>
Each component shown in Table 1 below was used in the composition (parts by mass) shown in the same table.
In this example, the adhesive composition was of a two-liquid type.
The polyisocyanate compound shown in Table 1 below was used as the main component of the two-component adhesive composition.
On the other hand, each curing agent was obtained by mixing components other than the polyisocyanate compound shown in Table 1 below.
The main agent and each curing agent obtained as described above were mixed with a stirrer to produce an adhesive composition.

<Evaluation (vulcanized rubber adhesion)>
Using each adhesive composition produced as described above, the following evaluation of vulcanized rubber adhesion (adhesion to vulcanized rubber) was performed. The results are shown in Table 1.

For evaluation of vulcanized rubber adhesion, first, vulcanized rubber was prepared as follows.
・Preparation of vulcanized rubber From the components shown in the following "rubber composition for vulcanized rubber", the components excluding sulfur and vulcanization accelerator were kneaded for 5 minutes in a 1.8 L closed type mixer and discharged to make a masterbatch. . A rubber composition was prepared by adding sulfur and a vulcanization accelerator to the obtained masterbatch and mixing with an open roll.
The rubber composition prepared as described above was vulcanized at 170° C. for 10 minutes in a mold of a predetermined shape to produce a vulcanized rubber.

((Rubber composition for vulcanized rubber))
・ 100 parts by mass of halogenated butyl rubber (brominated isobutylene isoprene rubber, manufactured by EXXON CHEMICAL)
・ 25 parts by mass of carbon black (Niteron #GN, N ₂ SA manufactured by Shin Nikka Carbon Co., Ltd. is 35 m ² /g
・ 3 parts by mass of zinc oxide (3 types of zinc oxide manufactured by Seido Chemical Industry Co., Ltd.)
・ Sulfur 3 parts by mass (Sulfax 5 manufactured by Tsurumi Chemical Industry Co., Ltd.)
・ 2 parts by mass of vulcanization accelerator (DM-PO manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)

- Preparation of test body - application process Each adhesive composition produced as described above was applied to the vulcanized rubber to a thickness of 1.0 mm.

Curing step The vulcanized rubber coated with the adhesive composition is placed under conditions of 25 ° C. and 50% relative humidity for 180 minutes to cure, and an adhesive layer (polyurethane adhesive) is formed on the vulcanized rubber by the adhesive composition. agent) was obtained.

· Cross-cut test The adhesive layer of the above specimen is cut at a pitch of 1 mm with a cutter knife to create 100 base meshes (10 rows × 10 columns), and cellophane adhesive tape (width 18 mm) was completely adhered, and immediately, a cross-cut peel test was performed in which one end of the tape was held perpendicular to the vulcanized rubber and instantaneously separated.
After the cross-cut peeling test, the number of base stitches remaining on the vulcanized rubber was examined.

·Evaluation Criteria When the number of base stitches remaining on the vulcanized rubber was 10 or more, it was evaluated as having excellent adhesion to the vulcanized rubber (to each other).
When the number of base stitches was 10 or more, it was evaluated that the larger the number, the more excellent the adhesiveness to vulcanized rubber (to each other).
When the number of base stitches was less than 10, it was evaluated as having poor adhesion to vulcanized rubber (to each other).

Details of each component shown in Table 1 are as follows.
Polyisocyanate compound Polymeric MDI: Polymeric MDI (trade name Sumidule 44V10, manufactured by Sumika Bayer Urethane) melting point -25°C (liquid at room temperature). Average number of isocyanate functional groups per molecule: 2.4

(ricinoleic acid glyceride)
• Ricinoleic acid glyceride 1 (carboxy-modified H-30): a castor oil-based polyol containing ricinoleic acid glycerides. The ricinoleic acid glycerides include ricinoleic acid triglycerides (which are mixtures of ricinoleic acid mono-, di- and triglycerides). The double bonds of the castor oil-based polyol (including the ricinoleic acid glyceride) are carboxy-modified. The number of functional groups per molecule (terminal hydroxyl groups; the number of functional groups does not include carboxyl groups) is 2.7. The content of the amount of ricinoleic acid glycerides in the castor oil polyol is 45% by weight. URIC H-30 manufactured by Ito Oil Co., Ltd. Molecular weight 700. Melting point -30°C.

(Comparative) Polypropylene glycol: Exenol PPG manufactured by AGC. Number average molecular weight 700. Melting point -65°C.
(Comparative) 1,6-hexanediol adipate: F7-67 manufactured by ADEKA. Number average molecular weight 1,000. Melting point 60°C. Polyester polyol of 1,6-hexanediol and adipic acid

(Plasticizer)
· Plasticizer 1 DINP: diisononyl phthalate (DINP), manufactured by J-Plus. SP value 16.5 (MPa) ^1/2 . Molecular weight 419.
· Plasticizer 2 Aroma oil: trade name Dianafrecia 32, manufactured by Idemitsu Petrochemical Co., Ltd. SP value 14.5 (MPa) ^1/2 . molecular weight 650

· Plasticizer 3 dimethylformamide: manufactured by Wako Pure Chemical Industries, Ltd. SP value 20.1 (MPa) ^1/2 . molecular weight 73; It corresponds to the compound A represented by the above formula (1).
· Plasticizer 4 Urea: manufactured by Wako Pure Chemical Industries, Ltd. SP value 22 (MPa) ^1/2 . molecular weight 60; It corresponds to the compound A represented by the above formula (1).

(filler)
- Filler 1 Bentonite: Product name: Kunipia, manufactured by Kunimine Industries. Purified bentonite Filler 2 Silica: trade name R923, manufactured by Nippon Aerosil Co., Ltd. Filler 3 Surface-treated calcium carbonate: trade name Kalfine 200, manufactured by Maruo Calcium Co., Ltd.

As is clear from the results shown in Table 1, when Comparative Example 1 containing polypropylene glycol instead of ricinoleic acid glyceride was applied to the vulcanized rubber, the adhesion to the vulcanized rubber was poor. .
When Comparative Example 2 containing no ricinoleic acid glyceride and instead containing 1,6-hexanediol adipate was applied to vulcanized rubber, the adhesion to vulcanized rubber was poor.

In contrast, the composition of the present invention was able to be applied to vulcanized rubber to adhere the vulcanized rubber.

Claims (12)

a polyisocyanate compound;
ricinoleic acid glyceride ;
and a compound A represented by the following formula (1) , wherein the double bond derived from ricinoleic acid in the ricinoleic acid glyceride may be modified,
A polyurethane adhesive composition applied to vulcanized rubber.
In formula (1), R ¹ is an amino group, a hydrogen atom, or a hydrocarbon group, and R ² and R ³ are each independently a hydrocarbon group optionally having a heteroatom, or a hydrogen atom. be. 2. The polyurethane-based adhesive composition according to claim 1, wherein the double bond derived from ricinoleic acid in said ricinoleic acid glyceride is modified. 3. The polyurethane-based adhesive composition according to claim 1, wherein the ricinoleic acid glyceride has a melting point of 35° C. or lower. The polyurethane-based adhesive composition according to any one of claims 1 to 3, wherein the polyisocyanate compound is liquid at room temperature. The polyurethane according to any one of claims 1 to 4, wherein the molar ratio (NCO/OH) of the isocyanate groups of the polyisocyanate compound to the hydroxyl groups of the ricinoleic acid glyceride is 0.3 to 1.8. adhesive composition. 6. The polyurethane-based adhesive composition according to any one of claims 1 to 5, further comprising a filler. 7. The polyurethane-based adhesive composition according to claim 6, wherein said filler is clay. 8. The polyurethane-based adhesive composition according to claim 6, wherein the content of said filler is 10 to 70% by mass relative to the total amount of said polyurethane-based adhesive composition. The polyurethane-based adhesive composition according to any one of claims 1 to 8 , wherein the compound A has an SP value of 20 (MPa) ^1/2 or more. The polyurethane-based adhesive composition according to any one of claims 1 to 9 , wherein the compound A has a molecular weight of 1,000 or less. The polyurethane-based adhesive composition according to any one of claims 1 to 10 , wherein the content of compound A is 1 to 20% by mass relative to the total amount of the polyurethane-based adhesive composition. 12. The polyurethane-based adhesive composition according to any one of claims 1 to 11 , wherein the ricinoleic acid glyceride has a substituent due to modification of double bonds derived from ricinoleic acid in the ricinoleic acid glyceride.