JPH04372684A - Adhesive resin composition - Google Patents

Abstract

PURPOSE:To impart high adhesive power in a wide temperature range to a wide variety of adherend materials. CONSTITUTION:An adhesive resin composition made by incorporating a polyfunctional isocyanate compound into a polyester-amide resin consisting of 20-99wt.% polyester units (a) formed from a glycol component comprising 10-80mol% ethylene glycol and 20-90mol% other glycol and a dibasic acid component comprising 20-100mol% aromatic dibasic acid and 0-80mol% other dibasic acid and 1-80wt.% polyamide units (b) comprising polydodecanamide and/or polyundecanamide.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to an adhesive resin composition, and more particularly, it relates to an adhesive resin composition containing a polyesteramide resin.
The present invention relates to an adhesive resin composition that has high adhesive strength over a wide temperature range to a wide range of adherends.

0002

[Prior Art] It is possible to bond metals, various plastics, glass, fibers, wood, paper, leather, etc., or to coat these materials to impart various functions.
In recent years, this method has been used in various industrial fields. One example of adhesive resin compositions used for such purposes is a composition using a copolymerized polyester resin. The following are known as examples of adhesive resin compositions using such copolymerized polyester resins. A composition containing as adhesive components a copolymerized polyester having branches in its molecular chain and a chain extender that reacts with the end groups of the polyester such as a diisocyanate compound was published in 1973.
It is disclosed in Japanese Patent No. 37974. In addition, an adhesive resin composition obtained by diluting a saturated polyester resin and an isophorone isocyanate compound with a solvent was disclosed in Japanese Patent Application Laid-Open No. 59-18
It is disclosed in Japanese Patent No. 7070.

0003

[Problem to be solved by the invention] Said Japanese Patent Publication Publication No. 48-37
The adhesive composition disclosed in JP-A No. 974 and the adhesive composition disclosed in JP-A-59-187070 have a certain degree of high adhesive strength, heat resistance over a wide temperature range, and flexibility. It is widely used as an adhesive for metal laminates, flexible printed wiring boards, polyester films for packaging, etc., as a coating agent for metals such as cans, and as a binder for magnetic tapes and inks. be. However, when the glass transition temperature of the resin is lowered in order to impart flexibility, the resin becomes amorphous and extremely flexible, resulting in a decrease in cohesive strength, not to mention adhesive strength at room temperature. In particular, sufficient adhesive strength cannot be obtained at high temperatures. Moreover, when the glass transition temperature of the resin is raised, the resin becomes hard and brittle, and the T-peel strength becomes relatively low and insufficient compared to the tensile shear strength.

Therefore, the present invention provides an adhesive resin composition that has high adhesion and adhesion to a wide range of adherends, maintains this over a wide temperature range, and is useful as adhesives, coatings, binders, etc. The challenge is to provide things.

[0005]

[Means for Solving the Problems] The above objects are achieved by an adhesive resin composition characterized by containing a specific polyesteramide resin (A) and a polyfunctional isocyanate compound (B).

That is, the present invention provides ethylene glycol 10
-80 mol%, other glycols 20-90 mol%, and aromatic dibasic acid 20-100 mol%.
Polyester unit (a) formed from a dibasic acid component consisting of mol% and 0 to 80 mol% of other dibasic acids (a) 20 to
99% by weight and polyamide units (b) 1 to 80 which are polydodecanamide and/or polyundecaneamide
It is an adhesive resin composition formed by blending a polyfunctional isocyanate compound (B) with a polyesteramide resin (A) consisting of % by weight.

The configuration of the present invention will be explained in detail below.

The polyesteramide resin (A) of the present invention consists of polyester units (a) and polyamide units (b).

The polyester unit (a) contains ethylene glycol in an amount of 10 to 80 mol%, preferably 20 to 70 mol%.
, other glycols 20-90 mol%, preferably 3
A glycol component consisting of 0 to 80 mol% and an aromatic dibasic acid of 20 to 100 mol%, preferably 40 to 95 mol%.
, other dibasic acids 0 to 80 mol%, preferably 5 to 6
It is synthesized from a dibasic acid component consisting of 0 mol%.

[0010] If the proportion of ethylene glycol in the total glycol component is less than 10 mol%, or
If it exceeds 0 mol%, the solubility in the solvent will be insufficient.

Other glycols used in combination with ethylene glycol include 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-
Propanediol, 1,3-butanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, diethylene glycol, neopentyl glycol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propane Examples include aliphatic glycols such as diols, alicyclic glycols such as 1,4-cyclohexanedimethanol, aromatic glycols such as ethylene oxide or propylene oxide adducts of bisphenol A, and ethylene oxide or propylene oxide adducts of bisphenol S. One or more of these can be selected and used. Among these, neopentyl glycol, 1,6-hexanediol, 1,
4-butanediol and the like are preferred.

[0012] If the proportion of the aromatic dibasic acid in the total dibasic acid component is less than 20 mol%, the adhesive strength will be low.

[0013] As the aromatic dibasic acid, terephthalic acid,
Examples include isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, and 4,4'-diphenyldicarboxylic acid, and one or more types thereof are selected and used. It is also possible to use lower alkyl esters. In order to obtain sufficient adhesive strength, it is preferable to use terephthalic acid as one of the aromatic dibasic acid components. Isophthalic acid can be mentioned as an aromatic dibasic acid preferably used in combination with terephthalic acid.

Other dibasic acids are used in an amount of 0 to 80 mol % based on the total dibasic acid components. Other dibasic acids include aliphatic dibasic acids and alicyclic dibasic acids.

Examples of aliphatic dibasic acids include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, α,ω-octadecanedicarboxylic acid, and dimer acid. Select and use one or more types from the following. Among these, adipic acid, sebacic acid, dodecanedioic acid, etc. are preferred.

Examples of the alicyclic dibasic acids include hydrogenated terephthalic acid, hydrogenated isophthalic acid, hydrogenated orthophthalic acid, and 2,6-
Examples include hydrogenated products of naphthalenedicarboxylic acid and hydrogenated products of 4,4'-diphenyldicarboxylic acid, and one or more of these may be selected and used. Among these, hydrogenated terephthalic acid and hydrogenated isophthalic acid are preferred. It is also possible to use aliphatic dibasic acids and alicyclic dibasic acids in combination.

The polyester unit (a) of the present invention is an amorphous copolymerized polyester which is a combination of ethylene glycol, a preferred glycol as described above, a preferred aromatic dibasic acid, and a preferred dibasic acid.

In some cases, it is also possible to copolymerize a small amount of trivalent or higher polycarboxylic acid and/or trivalent or higher polyol.

Examples of trivalent or higher polybasic acids include trimellitic acid and pyromellitic acid. Examples of polyols having a valence of 3 or more include glycerin, trimethylolpropane, and pentaerythritol. These polybasic acids and polyols are preferably used in an amount of 0 to 10 mol% relative to the dibasic acid or glycol.

Further, the polyamide unit (b) is polydodecanamide and/or polyundecaneamide, and 1
It is formed from 2-aminododecanoic acid and/or 11-aminoundecanoic acid.

The polyesteramide resin (A) of the present invention contains polyester units (a) in an amount of 20 to 99% by weight, preferably 40 to 95% by weight, particularly preferably 60 to 90% by weight.
and polyamide unit (b) 1 to 80% by weight, preferably 5 to 60% by weight, particularly preferably 10 to 40% by weight. When the polyester unit (a) is less than 20% by weight, solvent solubility decreases. Also polyamide unit (b)
If the amount is less than 1% by weight, the adhesive strength and heat resistance will decrease.

The polyester unit (a) and the polyamide unit (b) are present in the polyesteramide resin (A) in a statistical distribution depending on the copolymerization ratio.

The polyesteramide resin (A) used in the adhesive resin composition of the present invention is ethylene glycol, other glycols, aromatic dibasic acids or their lower alkyl ester derivatives, other dibasic acids or their lower alkyl esters. It is produced by melt polymerizing the derivatives, 12-aminododecanoic acid and/or 11-aminoundecanoic acid. To show a specific method, aromatic dibasic acid and other dibasic acid are mixed with 1.
About 150-2.0 times the molar amount of glycol and 12-aminododecanoic acid and/or 11-aminoundecanoic acid in the presence of a conventional esterification catalyst.
The reaction is carried out under normal pressure at a temperature of 240°C, or the reaction is carried out under pressure at a temperature of about 240 to 260°C without using a catalyst. When using lower alkyl ester compounds of aromatic dibasic acids and other dibasic acids as starting materials, approximately 1
The reaction is carried out under normal pressure at a temperature of 50 to 240°C. Then, heating polycondensation is carried out at 220 to 290° C. under reduced pressure of 10 mmHg or less, preferably 1 mmHg or less. At this time, it is preferable to use a polymerization catalyst. After carrying out an esterification reaction or transesterification reaction using only the components forming the polyester unit (a), adding 12-aminododecanoic acid and/or 11-aminoundecanoic acid forming the polyamide unit (b), After carrying out a preliminary reaction for 1 to 2 hours at 200 to 240°C under a nitrogen blanket, polycondensation may be carried out under reduced pressure. In addition, 1, which is the raw material for the polyamide unit (b)
Although it is preferable to use 2-aminododecanoic acid alone, a part thereof can also be used in the form of laurolactam.

[0024] Esterification catalysts include titanium compounds, tin compounds, lead compounds, etc.; transesterification catalysts include zinc compounds, manganese compounds, cobalt compounds, etc.
Examples of the polymerization catalyst include antimony compounds, titanium compounds, zinc compounds, tin compounds, and germanium compounds. When a phosphorus compound is used together with a polymerization catalyst, the polymerization reactivity and color tone of the polymer are further improved.

o-dichlorobenzene/phenol (
The reduced specific viscosity measured at a concentration of 1.0% using a mixed solvent with a volume ratio of 4/6) is preferably 0.1 to 1.2 dl/g.
, particularly preferably 0.5 to 1.0 dl/g. If the reduced specific viscosity is too small, the adhesive strength at low temperatures will be insufficient. Further, if the reduced specific viscosity is too large, the solvent solubility of the resin and the storage stability of the adhesive will be insufficient.

The polyesteramide resin of the present invention has a polyester unit with a specific chemical structure and an aliphatic polyamide unit in its molecular chain, and this effect improves adhesive strength.

The polyfunctional isocyanate compound (B) used in the present invention is a compound having at least two isocyanate groups. Preferred examples include aliphatic ones such as hexamethylene diisocyanate and its derivatives, alicyclic ones such as isophorone diisocyanate and its derivatives, and 2,4-tolylene diisocyanate, 2,6- Mention may be made of aromatic compounds such as tolylene diisocyanate and its derivatives, methylene-bis-phenylisocyanate and its derivatives. More preferable examples include adduct polyisocyanate compounds obtained by modifying these compounds into adducts, and polymerized polyisocyanate compounds obtained into polymers. In addition, blocked isocyanates whose isocyanate groups are masked with caprolactam or the like can also be used.

The adhesive resin composition of the present invention contains 1 to 30 parts by weight, preferably 2 to 2 parts by weight, of a polyfunctional isocyanate compound (B) per 100 parts by weight of the polyesteramide resin (A).
It is preferable to contain 0 parts by weight.

A curing catalyst, a pigment, a coloring agent, a leveling agent, a weathering agent, an antioxidant, etc. may be added to the adhesive resin composition of the present invention, if necessary.

The adhesive resin composition of the present invention is generally used after being dissolved in an organic solvent. Organic solvents include toluene, xylene, "Solvesso"#100,"Solvesso"#150, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, n-butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, isophorone, butanol, octanol, butyl. It can be arbitrarily selected from carbitol and the like depending on its solubility, evaporation rate, economical efficiency, etc.

[0031]

[Examples] The present invention will be explained below with reference to Examples. Note that all parts in the examples are based on weight.

[0032] Each measurement item shown in the Examples and Comparative Examples was carried out according to the following method.

・Glass transition temperature Measured by DSC.

・Reduced specific viscosity resin 0.25g was mixed with o-dichlorobenzene/phenol (
It was dissolved in 25 ml (volume ratio 4/6) and measured at 25°C.

Reference Examples 1 to 5 175 parts of terephthalic acid, 175 parts of isophthalic acid, 107 parts of sebacic acid, 123 parts of ethylene glycol, 1,6-
172 parts of hexanediol was charged into a reaction vessel equipped with a stirrer and a rectifying tube, and an esterification reaction was carried out at 240° C. for 4 hours under pressure. Next, it was transferred to a reaction vessel equipped with a helical ribbon stirring blade that had been sufficiently purged with nitrogen, and 437 parts of 12-aminododecanoic acid was added thereto, and a preliminary reaction was carried out at 240°C for 1 hour. 0.1 part of antimony oxide,
After adding 0.1 part of phosphoric acid, the reaction conditions were brought to 275° C. and 1 mmHg or less over about 1 hour according to a temperature increase and pressure reduction program. Polycondensation reaction was carried out in this state for 1 hour and 50 minutes to obtain a pale yellow transparent polyesteramide resin (A-1). Polyesteramide resin (A-1)
The glass transition temperature of is -38℃, and the reduced specific viscosity is 0.56d.
l/g. The proportion of polyamide units consisting of polydodecanamide determined by elemental analysis is 40% by weight, and the composition ratio of polyester units determined from 1H-NMR spectrum is that the acid components are terephthalic acid/isophthalic acid/sebacic acid = 40/40. /20 (molar ratio), and the glycol component was ethylene glycol/1,6-hexanediol = 50/50 (molar ratio). Hereinafter, in the same manner, polyesteramide resins (A-2) to (
A-5) was produced.

[0036]

[Table 1]

Reference Examples 6 to 11 In the same manner as in Reference Example 1, polyesteramide resins (A-6) to (A-8) shown in Table 2 and copolymerized polyester resins 1 to 2 containing no polyamide units were produced. did.

[0038]

[Table 2]

Examples 1-2 Polyesteramide resin (A-1) or (A-2)
, methyl ethyl ketone/toluene (weight ratio 20/80
) Add to the mixed solvent so that the solid content concentration is 30% by weight,
It was heated to 60°C to dissolve it. After cooling this solution to room temperature, a polyfunctional isocyanate compound "Coronate" 2030 (manufactured by Nippon Polyurethane Industries) was added so that the solid content of the isocyanate compound was 5 parts per 100 parts of the solid content of the resin. and stirred to obtain a homogeneous solution. This solution was applied to two degreased cold-rolled steel plates with a thickness of 0.5 mm.
Coating was performed using a bar coater so that the dry coating thickness was 25 μm. After drying in a hot air oven at 180°C for 2 minutes, these steel plates were glued together and heated at 200°C for 5k.
Hot pressing was performed for 1 minute under a pressure of g/cm2. After heat treatment at 100°C for 24 hours, it was left at room temperature for 1 day, and the tensile shear strength of the 25 mm x 10 mm overlapped portion was measured at -20°C, 25°C, 50°C, and 100°C.
Measurement was performed at a tensile speed of 20 mm/min. The results are shown in Table 3.

As is clear from Table 3, the adhesive resin composition of the present invention has high adhesive strength over a wide temperature range.

Comparative Examples 1-3 Polyesteramide resin (A-1) used in Examples 1-2
) or (A-2), the same adhesion test as in Examples 1 and 2 was conducted without blending the polyfunctional isocyanate compound. Further, an adhesion test similar to that in Example 1 was conducted using a copolymerized polyester resin (2) having a similar glass transition temperature in place of the polyesteramide resin (A-1). The results are shown in Table 3.

As is clear from Table 3, when the polyesteramide resin is not blended with a polyfunctional isocyanate compound or when a copolymerized polyester resin is used instead of the polyesteramide resin, the adhesive strength at room temperature is low;
Furthermore, when the measurement temperature is increased, the adhesive strength decreases significantly.

[0043]

[Table 3]

Example 3 Polyesteramide resin (A-5) was added to methyl ethyl ketone at a solid content of 30% by weight, and the mixture was heated at 60°C.
It was heated to dissolve. After cooling this solution to room temperature,
"Coronate" L (manufactured by Nippon Polyurethane Industries), a polyfunctional isocyanate compound, was added so that the solid content of the isocyanate compound was 15 parts per 100 parts of the solid content of the resin, and stirred to form a uniform solution. did. Apply this solution to PET film with a thickness of 0.1 mm, soft PVC film with a thickness of 0.5 mm, and aluminum foil with a thickness of 0.5 mm using a bar coater so that the coating thickness after drying is 30 μm. It was applied using. After drying in a hot air oven at 100°C for 2 minutes, the surfaces coated with the adhesive composition of each adherend were glued together and heat pressed at 160°C for 1 minute under a pressure of 1 kg/cm2. Ta. After being left at room temperature for one day, the T-peel strength of the overlapping portion of 25 mm x 50 mm was measured at 25° C. and at a tensile rate of 50 mm/min. The results are shown in Table 4.

As is clear from Table 4, the adhesive resin composition of the present invention has high adhesive strength to various adherends.

Comparative Examples 4 to 5 No polyfunctional isocyanate compound was added to the solution of the polyesteramide resin (A-5) used in Example 3.
An adhesion test similar to Example 3 was conducted. In addition, Example 3
An adhesion test similar to that was conducted. The results are shown in Table 4.

As is clear from Table 4, when a polyfunctional isocyanate compound is not blended with the polyester amide resin, or when a copolymerized polyester resin is used instead of the polyester amide resin, there is no effect on any adherend. Adhesion strength is low.

[0048]

[Table 4]

Examples 4-5 Polyesteramide resin (A-3) or (A-4)
To 100 parts, 10 parts of 2,4-tolylene diisocyanate was added, and methyl ethyl ketone was added so that the solid content concentration was 30% by weight, and the mixture was dissolved by shaking vigorously at room temperature. This solution was applied to a PET film with a thickness of 0.1 mm using a bar coater so that the coating thickness after drying was 50 μm. After drying in a hot air oven at 100°C for 2 minutes, the Tetron tricot cloth was glued together and heated to 150°C.
Heat pressing was carried out at 0.5 kg/cm2 for 1 minute at a temperature of 0.5 kg/cm2. After leaving it at room temperature for a day, 25mm x 50
The T-peel strength of the overlapped portion of mm was measured at 25° C. and a tensile speed of 50 mm/min. The results are shown in Table 5.

As is clear from Table 5, the adhesive resin composition of the present invention has high adhesive strength.

Comparative Examples 6 to 9 Instead of the polyesteramide resin (A-4) used in Example 5, polyesteramide resins (A-6) and (A-
7) and (A-8), 2,4-
10 parts of tolylene diisocyanate were added, and methyl ethyl ketone was added so that the solid content concentration was 30% by weight, followed by vigorous shaking at room temperature. Since no dissolution occurred even after 3 hours had passed, the temperature was raised to 60°C, but no dissolution occurred. Further, an adhesion test similar to that in Example 4 was conducted using a copolymerized polyester resin (1) having a similar glass transition temperature in place of the polyesteramide resin (A-3). The results are shown in Table 5.

As is clear from Table 5, when a copolymerized polyester resin is used instead of a polyesteramide resin, the adhesion force to this adherend is also low.

[0053]

[Table 5]

[0054]

Effects of the Invention The adhesive resin composition of the present invention has high adhesive strength over a wide temperature range to a wide range of adherends.

Claims (1)

[Claims] Claim 1: A glycol component consisting of 10 to 80 mol% of ethylene glycol and 20 to 90 mol% of other glycols, and 20 to 100 mol% of aromatic dibasic acids and 0 to 80 mol% of other dibasic acids. A polyesteramide resin (A) consisting of 20 to 99% by weight of a polyester unit (a) formed from a dibasic acid component and 1 to 80% by weight of a polyamide unit (b) of polydodecanamide and/or polyundecaneamide. , an adhesive resin composition containing a polyfunctional isocyanate compound (B).