JP6048801B2 - Polyamide polyamine condensate, polyamide polyamine crosslinkable modified product, curing agent for epoxy resin, cured epoxy resin, aqueous adhesive composition and wet paper strength agent - Google Patents

Description

The present invention relates to a polymerized rosin-based polyamide polyamine condensate, a crosslinkable derivative thereof, and uses thereof, which are environmentally friendly and have various characteristics.

Polyamide polyamine condensates are known to be used as curing agents for epoxy resins, and compositions and cured products comprising the curing agents and epoxy resins can be applied to various applications such as paints and adhesives. Known (for example, Patent Document 1).

Further, a crosslinkable modified product, which is a reaction product of a polyamide polyamine condensate and an epihalohydrin, is used, for example, as a component of an aqueous adhesive (for example, Patent Document 2), and improves the strength of paper products when wet. Have been used in applications such as wet paper strength agents (for example, Patent Documents 3 to 5).

  In recent years, in response to requests for environmental protection and environmental considerations, development efforts have been made in various fields, such as synthesis technology for new bio-based plastics using biomass and greening technology focusing on natural materials.

  However, a composition in which a natural material is simply blended generally tends to lower performance such as strength and water resistance. Therefore, it is desirable to introduce a natural material as a reaction component rather than a blending component. By the way, fatty acids and rosin are listed as natural materials. Since these are monofunctional carboxylic acids, they can be introduced as side chains and terminal parts of various plastics and resins, but are easy to introduce into the main chain. It was not. For this reason, for example, attempts have been made to incorporate rosin into a main chain by modifying it with an unsaturated fatty acid, polymerizing or dimerizing it into a polyfunctional compound. However, since the purity of the polymer or dimerized product is low, there is a problem that the obtained target product cannot exhibit desired performance.

  Therefore, in this field, the development of a target product obtained from a natural material, which is inferior to a use product obtained from a conventional petroleum material, is eagerly desired.

JP-A-8-73570 ([0030]) JP-A-60-124675 JP-A-5-209159 ([0008]) Japanese Patent Laying-Open No. 2005-208456 ([0056]) Japanese Patent Laid-Open No. 6-1842 ([0002])

An object of the present invention is to provide a polyamide polyamine condensate comprising a polymerized rosin component, which is a natural material, and a crosslinkable modified product thereof from the viewpoint of environmental considerations, and an object thereof is to utilize them for various applications.

In order to solve the above-mentioned problems of the prior art, the present inventor has intensively studied paying attention to the correlation between the amount or purity of the polymerized rosin or its lower ester and the performance of the target product. As a result, a polyamide polyamine condensate containing a specific amount or more of the polymerized rosin or a crosslinkable modified product of the condensate can solve the above problems, and further a polymerized rosin containing a specific amount or more of a dimerization product The present inventors have found that a polyamide polyamine condensate using a polymer and a crosslinkable modified product of the condensate can solve the above problems more suitably, and have completed the present invention.

That is, the present invention is a polyamide polyamine condensate obtained by condensing a dicarboxylic acid component and a polyalkylene polyamine component, and contains 20 mol% or more of polymerized rosin and / or polymerized rosin lower ester in the dicarboxylic acid component. The present invention relates to a polyamide polyamine condensate (A) characterized by being. The present invention also relates to a polyamide polyamine crosslinkable modified product (B) obtained by reacting the polyamide polyamine (A) with epihalohydrin. Moreover, this invention concerns on the hardening | curing agent for epoxy resins which comprises a polyamide polyamine condensate (A). Moreover, this invention relates to the epoxy resin hardened | cured material obtained by hardening an epoxy resin using the said hardening | curing agent for epoxy resins. The present invention further relates to an aqueous adhesive composition and a wet paper strength agent comprising the polyamide polyamine crosslinkable derivative (B).

According to the present invention, a polyamide polyamine condensate (A) and a polyamide polyamine crosslinkable derivative (B) which are environmentally friendly and excellent in various properties can be provided. The polyamide polyamine condensate (A) obtained in the present invention can be used for various uses, for example, for epoxy resin cured products (paints, adhesives, etc.) as a curing agent for epoxy resins. The polyamide polyamine crosslinkable modified product (B) of the present invention is suitable for, for example, an aqueous adhesive composition, a wet paper strength agent, and the like. In addition, the applications using the condensate (A) and the crosslinkable modified product (B) of the present invention are not inferior in terms of performance compared to conventional petroleum-based applications, and for purposes such as environmental protection. It also contributes.

The polyamide polyamine condensate (A) of the present invention (hereinafter referred to as condensate (A)) is composed of a dibasic acid and / or a derivative thereof (hereinafter referred to as dicarboxylic acid component) and a polyalkylene polyamine (hereinafter referred to as polyamine). Component)) containing a polymerized rosin and / or polymerized rosin lower ester (hereinafter referred to as polymerized rosin) in a total of 20 mol% or more in the dicarboxylic acid component, preferably It contains 40 mol% or more. In the polymerized rosin lower ester, “lower” means a methyl, ethyl, or propyl group.

The polymerized rosins used in the present invention are not particularly limited, but the content of the dimerized product (dimerized rosin, dimerized rosin lower ester) is 40% by weight or more, preferably 50% by weight or more, more preferably 80%. It is good to use what is weight% or more. When the color tone is important in the intended use, it is more preferable to use polymerized rosins starting from distilled rosin, hydrides, etc. as the polymerized rosins. It does not specifically limit as a manufacturing method of the said polymerized rosins, A well-known various method is employable.

As the dibasic acid, in addition to polymerized rosin, which is a characteristic part of the present invention, for example, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid Acids: aromatic dibasic acids such as phthalic acid, isophthalic acid and terephthalic acid. Examples of the dibasic acid derivative include the polymerized rosin lower ester, which is a characteristic part of the present invention, and the dibasic acid anhydride and lower ester. As these dicarboxylic acid components, it is necessary to use polymerized rosins in a specific amount or more as described above, but other dicarboxylic acid components can be used arbitrarily, and any one of them can be used alone or in combination as appropriate. Used.

Examples of the polyamine component used in the condensate (A) include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and iminobispropylamine. These polyamine components can be used alone or in appropriate combination.

The condensate (A) can be easily produced by subjecting the dicarboxylic acid component and the polyamine component to dehydration condensation or dealcoholization condensation by a known method. For example, the reaction may be carried out in the presence or absence of a catalyst such as sulfuric acid, benzenesulfonic acid, paratoluenesulfonic acid and the like at a reaction temperature of about 110 to 250 ° C. for about 2 to 24 hours. The use ratio of the dicarboxylic acid component and the polyamine component is not particularly limited, but it is usually preferable that the former: the latter is used in the range of about 1: 0.9 to 1.2 (molar ratio).

The properties and general constants of the condensate (A) are not particularly limited, and may be appropriately set depending on the application. The weight average molecular weight of the condensate (A) is usually about 1000 to 3000, preferably 1200 to 2500. The amine value of the condensate (A) is about 10 to 50 mgKOH / g, preferably 20 to 40 mgKOH / g in terms of solid content. If the amine value is less than the lower limit value, the curability of the epoxy resin tends to decrease. If the amine value is greater than the upper limit value, the adhesive strength of the resulting epoxy cured product tends to decrease. There is. The condensate (A) is preferably in the form of an aqueous liquid in the reaction with the epihalohydrin in the production of the polyamide polyamine crosslinkable modified product (B) described later. The aqueous liquid is an aqueous solution or an aqueous dispersion. Say. In addition to water, examples of the solvent used in the aqueous liquid include lower alcohols such as ethyl alcohol and isopropyl alcohol.

The polyamide polyamine crosslinkable modified product (B) of the present invention (hereinafter referred to as modified product (B)) is obtained by reacting the condensate (A) with epihalohydrin. As the epihalohydrin, for example, epichlorohydrin, epibromohydrin, or the like is used. The ratio of the epihalohydrin to the condensate (A) is not particularly limited, but from the viewpoint of reducing the amount of low-molecular organic halogen compound produced, the secondary amino group of the condensate (A) and the epoxy of epihalohydrin are usually used. It is preferably used so that the equivalent ratio of groups (epoxy group / secondary amino group) is in the range of 0.8 to 2.0. In order to reduce the amount of low-molecular organic halogen compound produced, the equivalent ratio is more preferably 1.5 or less, and the storage stability of the resulting modified product (B) as an aqueous liquid, Considering various performances (adhesiveness, water resistance effect, wet paper strength effect, etc.), the equivalent ratio is more preferably 0.9 or more.

The properties and general constants of the modified product (B) are not particularly limited, and may be appropriately set according to the application. When the modified product (B) is used in, for example, an aqueous adhesive or a wet paper strength agent, the molecular weight is not particularly limited, but the viscosity of a 50 wt% aqueous liquid at 25 ° C. is about 100 to 1000 mPa · s. It is preferable in terms of handleability and performance.

The reaction of the condensate (A) with epihalohydrin includes a step of adding epihalohydrin to the condensate (A) and a step of further thickening by crosslinking. The reaction temperature is usually preferably about 5 to 80 ° C., and the reaction solution is usually preferably about 20 to 70% by weight. Although such reaction conditions can be adjusted as appropriate, the reaction temperature is a temperature at which epihalohydrin is added to the condensate (A) (5 to 40) because it is easy to suppress the formation of low molecular weight organic halogen compounds and the control of the reaction is easy. It is preferable to carry out by setting in two stages, namely, (C: primary heat retention) and a temperature for further thickening (40-80 ° C .: secondary heat retention). When the reaction temperature is set in two stages, it is preferable that the concentration of the reaction solution is equal to or lower than the concentration of the secondary temperature compared to the concentration of the primary temperature. The concentration of the reaction solution is preferably adjusted to, for example, about 30 to 70% by weight for the primary heat retention and about 20 to 40% by weight for the second heat retention.

The condensate (A) of the present invention is suitable as a curing agent for epoxy resins. The applied epoxy resin is not particularly limited, and various known ones can be used. For example, novolac type epoxy resin, trisphenol epoxy resin, biphenyl type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, etc. are used alone. It may be used in combination of two or more. The blending ratio of the curing agent with respect to the epoxy resin is not particularly limited, but is usually about 10 to 150 parts by weight, preferably 20 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin in terms of solid content. The In other words, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly 0.7 to 1.2 equivalents as the residual amino group of the curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin. preferable.

Moreover, when preparing the said epoxy resin composition, you may use various well-known hardening accelerators as needed. For example, imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2- (dimethylaminomethyl) phenol, and triphenylphosphine compounds can be used. These may be used alone or in combination of two or more. When a curing accelerator is used, the amount used is preferably in the range of 0.01 to 15 parts by weight, particularly preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin. Moreover, in the said preparation, the viscosity of an epoxy resin composition can be suitably adjusted using various well-known organic solvents as needed.

The condensate (A) of the present invention can provide an epoxy resin cured product having excellent heat resistance as compared with, for example, a fatty acid dimer-based polyamide polyamine condensate. The reason for the manifestation of the effect seen in the condensate (A) is not clear, but it seems to be due to the use of a structurally bulky polymerized rosin as a dicarboxylic acid component in a specific amount or more.

The modified product (B) of the present invention can be suitably used as a blending component in various aqueous adhesive compositions. Specifically, water-resistant agents added to starch-based aqueous adhesives, curing agents applicable to water-soluble epoxy compounds, water-resistant agents that can be used in combination with synthetic resin emulsions, adhesive components for polarizing plates, etc. However, it is not limited to these. Although the usage-amount of the modified | denatured material (B) in an aqueous adhesive composition cannot be generally limited, for example, when using as a water-proofing agent for starch-type aqueous adhesives, it is usually 0.00 with respect to 100 weight part of starch. It is about 1 to 15 parts by weight (in terms of solid content), preferably 1 to 10 parts by weight. In addition, when used as a water-proofing agent that can be used in combination with a synthetic resin emulsion or the like, it is usually about 0.1 to 30 parts by weight (in terms of solid content) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion, preferably It mix | blends in the ratio of 1-20 weight part.

The modified product (B) of the present invention is suitable as a wet paper strength agent. For example, not only pulp fiber papermaking but also fibers and mineral fibers (asbestos, rock wool, etc.) and synthetic fibers (polyamide, polyester, polyolefin) Etc.) can be advantageously applied in the production of paper, paperboard, fiberboard and the like. The amount of the modified product (B) used, as in the case of known wet paper strength agents, varies depending on the use of the paper, so it is necessary to determine it appropriately according to the use. 0.05 to 1.0 part by weight is appropriate.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified.

Example 1 (Synthesis of polyamide polyamine condensate (A))
In a reactor equipped with a thermometer, a condenser, a stirrer and a nitrogen introduction tube, 420 parts (1 mole) of polymerized rosin (dimer content: 40%), 584 parts (4 moles) of adipic acid and 516 parts of diethylenetriamine ( 5 moles), the temperature was raised to 180 ° C. under a nitrogen stream, and the condensation reaction took about 8 hours while removing the generated water out of the system to obtain a polyamide polyamine condensate having a weight average molecular weight of 1600. (Referred to as A-1). Then, it was diluted with a predetermined amount of water to obtain a polyamide polyamine condensate aqueous solution having a solid content of 50% and a viscosity of 300 mPa · s (25 ° C.) (referred to as A-1 ′).

Examples 2 to 4 (Synthesis of polyamide polyamine condensate (A))
In Example 1, various polyamide polyamine condensates (A) were obtained in the same manner except that the type of polymerized rosin and the usage ratio thereof were changed as shown in Table 1 to obtain various polyamide polyamine condensates (A in order). -2 to A-4). Subsequently, these were diluted with water, and various condensate (A) aqueous liquids were obtained (in order, A-2 ′ to A-4 ′). These weight average molecular weights and viscosities are shown in Table 2.

In Table 1, the polymerized rosin No. 1 is the one used in Example 1, No. 2 is the dimerized product content of 50%, and No. 3 is the dimerized product content of 40%. It is hydrogenated.

Comparative Example 1 (Synthesis of polyamide polyamine condensate for comparison)
A reactor similar to that used in Example 1 was charged with 730 parts (5 moles) of adipic acid and 516 parts (5 moles) of diethylenetriamine, heated to 180 ° C. under a nitrogen stream, and the generated water was removed from the system. About 8 hours were required for the condensation reaction to obtain a comparative polyamide polyamine condensate (referred to as AC-1). Subsequently, it diluted with the predetermined amount of water, and obtained the polyamide polyamine condensate aqueous liquid for a comparison (it is called AC-1 '). These weight average molecular weights and viscosities are shown in Table 2.

Comparative Example 2 (Synthesis of polyamide polyamine condensate for comparison)
In a reactor similar to that used in Example 1, 1122 parts (2 moles) of fatty acid dimer, 438 parts (3 moles) of adipic acid, and 516 parts (5 moles) of diethylenetriamine were heated to 180 ° C. under a nitrogen stream. A condensation product for comparison was obtained by carrying out a condensation reaction taking about 8 hours while removing the produced water out of the system (referred to as AC-2). Subsequently, it diluted with the predetermined amount of water, and obtained the polyamide polyamine condensate aqueous liquid for a comparison (it is called AC-2 '). These weight average molecular weights and viscosities are shown in Table 2.

Example 5 (Synthesis of polyamide polyamine crosslinkable modified product (B))
540 parts of A-1 ′ obtained in Example 1 and 238 parts of water were prepared (adjusted to a reaction solution concentration of 40%) in the same reaction apparatus as used in Example 1, and the system temperature was maintained at 15 ° C. Then, 92 parts of epichlorohydrin (epoxy group of epichlorohydrin: secondary amino group of polyamidopolyamine (equivalent ratio) = 1.1: 1) was added dropwise over 2 hours, and then at 30 ° C. for 5 hours. Keep warm. Next, after adding 90 parts of water, the temperature was raised to 60 ° C. and kept for 2 hours. Further, 423 parts of water and 50 parts of 62.5% sulfuric acid were added and cooled to obtain a polyamide polyamine-epichlorohydrin resin aqueous solution having a solid content concentration of 25%, a viscosity of 250 mPa · s (25 ° C.), and a pH of 3.0. (Referred to as modified product B-1).

Examples 6-8
In Example 5, the reaction was carried out in the same manner except that the amount of A-1 ′ and the amount used was changed to the kind and amount of the condensate aqueous solution as shown in Table 3, and modified with polyamide polyamine-epichlorohydrin. A product aqueous solution was obtained (in order, modified products B-2 to B-4). Table 4 shows the solid content concentration, viscosity, and pH.

Comparative Examples 3-4
In Example 5, the reaction was carried out in the same manner except that A-1 ′ and the amount used were changed as shown in Table 3 to obtain a comparative polyamide polyamine-epichlorohydrin modified aqueous solution ( In this order, they are referred to as modified products BC-1 and BC-2). Table 4 shows the solid content concentration, viscosity, and pH.

Hereinafter, performance evaluation examples in specific applications using the condensate and the crosslinkable modified product of the present invention will be shown.

(Preparation of epoxy resin adhesive composition)
Regarding the modified products (A-1 to A-4) obtained in Examples 1 to 4 and the modified products for comparison (AC-1 and AC-2) obtained in Comparative Examples 1 and 2, bisphenol A type epoxy resins (100 parts by Japan Epoxy Resin Co., Ltd., trade name “EP828”) 50 parts and 1 part of a curing accelerator (triphenylphosphine) are blended and mixed uniformly, and curing conditions (150 ° C. × 2 Time + 180 ° C. × 8 hours) to obtain a resin molded body. The glass transition temperature (TMA temperature increase rate 2 ° C./min) and heat distortion temperature (based on JIS K7207) of the cured product thus obtained were measured. The results are shown in Table 5.

From Table 5, the epoxy resin cured product using the condensate of each example shows higher values for both the glass transition temperature and the heat distortion temperature than the epoxy resin cured product for comparison, and is excellent in cured product characteristics. it is obvious.

(Preparation of aqueous adhesive composition)
The modified products (B-1 to B-4) obtained in Examples 5 to 8 and the modified products for comparison (BC-1 and BC-2) obtained in Comparative Examples 3 to 4 were water resistant by the following method. Adhesives were prepared and their performance as waterproofing agents were evaluated. The results are shown in Table 6.

240 parts of corn starch was suspended in 585 parts of warm water at 40 ° C., then 44.6 parts of a 15% aqueous sodium hydroxide solution was added, and then 3.2 g of boric acid was added to obtain a paste solution. To this, 150 parts of styrene butadiene latex (solid content 51%, Tg-5 ° C., average particle diameter 130 nm) and 24 parts of the modified product as a water-resistant agent were added to prepare a water-resistant adhesive. The obtained adhesive is 10 g / m ² in terms of solid content on the top of a single-sided cardboard having a basis weight of 200 g / m ² and a water-resistant core with a water repellency (JIS P8137) R0 bonded thereto. Then, a water-resistant liner SK was bonded thereto and thermocompression bonded (160 ° C. × 5 seconds). After bonding, the corrugated cardboard sheet is allowed to stand for 24 hours at a temperature of 23 ° C. and a humidity of 50%. Based on JIS-Z-0402, the normal state adhesive strength and water-resistant adhesive strength ) Was measured.

From Table 6, it is clear that the aqueous adhesive composition using the modified product of each example is superior in both normal adhesive strength and water-resistant adhesive strength as compared with the comparative aqueous adhesive composition. The superiority as a waterproofing agent is recognized.

(Performance evaluation as wet paper strength agent)
The modified products (B-1 to B-4) obtained in Examples 5 to 8 and the modified products for comparison (BC-1 and BC-2) obtained in Comparative Examples 3 to 4 were wetted by the following method. The performance as a paper strength agent was evaluated. The results are shown in Table 7.

(Wet paper strength)
The pulp (L-BKP / N-BKP = 1/1) was disaggregated, and 0.4% (vs. pulp solid content conversion) of the above-mentioned crosslinking reaction product was added to the pulp slurry beaten until the filtrate amount reached 500 ml. . The pulp slurry thus obtained was paper-made with a TAPPI standard sheet machine (square) so as to have a basis weight of 60 g / m ² . The obtained wet paper was press dehydrated with a roll press at a linear pressure of 15 kg / cm. Subsequently, it dried for 4 minutes at 110 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. The hand-sheet was prepared by adjusting the humidity for 24 hours under the above conditions. The wet paper strength (breaking length: Km) of the obtained handsheet was measured according to JIS P8135.

From Table 7, it is clear that the wet paper strength agent of the present invention containing the modified product of each example can improve the wet strength as compared with the comparative example.

Claims (7)

A polyamide polyamine condensate obtained by condensing a dicarboxylic acid component and a polyalkylene polyamine component, wherein the dicarboxylic acid component contains 20 mol% or more of a polymerized rosin and / or a polymerized rosin lower ester. Polyamide polyamine condensate (A). 2. The polyamide polyamine condensate (A) according to claim 1, wherein the polymerized rosin and / or polymerized rosin lower ester contains 40% by weight or more of dimerized rosin and / or dimerized rosin lower ester. A polyamide polyamine crosslinkable modified product (B) obtained by reacting the polyamide polyamine condensate (A) according to claim 1 or 2 with an epihalohydrin.
A curing agent for epoxy resin comprising the polyamide polyamine condensate (A) according to claim 1 or 2. The epoxy resin hardened | cured material obtained by hardening an epoxy resin using the hardening | curing agent for epoxy resins of Claim 4. An aqueous adhesive composition comprising the polyamide polyamine crosslinkable modified product (B) according to claim 3. A wet paper strength agent comprising the polyamide polyamine crosslinkable modified product (B) according to claim 3.