JP2022014668A - Printing ink using bio-polyurethane resin - Google Patents

Abstract

To provide: a bio-polyurethane resin suitable for a varnish for printing ink, which maintains characteristics of the conventional bio-polyurethane resin, has a problem suppressed, the problem being thickening of a mixture when a hardener is added to an ink and, at the same time, has excellent heat resistance (hot peel strength); a bio-polyurethane resin solution; and a printing ink.SOLUTION: Provided is a bio-polyurethane resin containing a polymerization component in which an amount of a bio-derived component accounts for 35 mass% or more. The polymerization component comprises a polyol component (A), an isocyanate component (B), and a polyamine component (C). Further, the polymerization component contains a specific monoamine component (D) containing one amino group having an active amino group active hydrogen(s) and another active hydrogen group(s). The bio-polyurethane resin has a polyurethane-polyurea structure where a portion of a terminal amino group of a terminal active amino group-type polyurethane resin is substituted by another active hydrogen group and has an average number per one resin molecule of amino groups of 1.00 to 1.90.SELECTED DRAWING: None

Description

The present invention relates to a biopolyurethane resin, a biopolyurethane resin solution, a method for producing a biopolyurethane resin, and a printing ink using these. More specifically, the present invention relates to a technique for providing a biopolyurethane resin useful for a varnish for printing ink.

In recent years, biological resources (biomass) other than fossil resources have been attracting attention as industrial resources that are not depleting resources. In particular, plants grow by absorbing CO ₂ in the atmosphere through photosynthesis using sunlight as energy, so products that commercialize biological raw materials (biomass plastics, synthetic fibers, printing ink, etc.) grow plants. It is thought that the amount of CO ₂ absorbed by photosynthesis in the process and the amount of CO ₂ emitted by incineration of plants are offset and do not affect the increase or decrease of CO ₂ in the atmosphere (carbon neutral), and its development is expected. There is. Among the products using biological raw materials, the biomass mark certified products, which will be described later, are desired to be developed and used because they are safe, contribute to the formation of a recycling-oriented society, and help prevent global warming.

The polyurethane resin is basically obtained by reacting a high-molecular-weight polyol component, an organic polyisocyanate component, and, if necessary, a polyamine chain extender component, but the type and combination of each of these components. It is possible to provide a polyurethane resin having various performances (physical properties) by changing the above. For example, a printing ink using a polyester-based polyurethane resin solution containing an active amino group at the terminal as a varnish for printing ink is useful in terms of excellent adhesion performance to various plastic substrates and pigment dispersibility.

However, most printing inks that use polyurethane resin for varnish have a life cycle in which raw materials are procured from petroleum resources, materials are manufactured, used, and finally incinerated as garbage. It has been demanded. On the other hand, printing inks that take ecological considerations into consideration have been sufficient in terms of "biomass degree," which indicates the amount of biological resources, in addition to conventional functionality such as adhesiveness, pigment dispersibility, and printability. It wasn't. Recently, in addition to polypropylene films as bio-derived biomass films, polyethylene terephthalate (PET), nylon (NY), which use bio-derived raw materials and are applicable to flexible packaging applications such as food packaging, have been used. Bioplastic films such as polypropylene (PP) and polyethylene (PE) films are beginning to be marketed. There is also a demand for biomass conversion in the ink layer formed on these new biomass plastic base materials.

In addition to the demand for biomass conversion of printing inks, non-toluene solvent-based or non-toluene non-MEK solvent-based varnishes for printing inks that do not use toluene or methyl ethyl ketone (MEK) solvent are required. Further, even when a biopolyurethane resin containing a biological raw material is used for a printing ink varnish, or even when a non-toluene solvent-based or non-toluene non-MEK solvent-based printing ink varnish is used, the conventional varnish is used. Similar to the case where a petroleum-derived polyurethane resin is used, there is a demand for a printing ink having high adhesive strength, excellent pigment dispersibility, and excellent printability.

In contrast to the above-mentioned current situation, as a varnish for printing ink using a biological component as a manufacturing raw material, for example, a polyurethane resin using a polyester polyol made of a biological dimer acid is known (Patent Document 1). Further, a printing ink (Patent Document 2) is also known in which printing suitability such as plate jamming is improved by using a polyurethane resin in which the amount of polyester made of biologically-derived dimer acid is reduced.

On the other hand, as mentioned earlier, the use of biomass is being considered on a global scale, and the development of printing inks that use polyurethane resin with excellent functionality and biomass for printing ink varnishes is expected and realized. If possible, it is extremely useful. In addition, due to technological trends in recent years, when the biomass content in the solid content of printing ink is 10% by mass or more, by satisfying other requirements such as safety and security as an environmental product, the "Biomass Mark" from the Japan Organic Resources Association There is a background of social norms, such as being certified. In order to receive this certification, an industrially usable biopolyurethane resin that achieves a high biomass content of 35% by mass or more, more preferably 40% by mass or more in the polyurethane resin used as a raw material for varnish for printing ink is required. It is necessary, and its technological development is awaited.

However, the ink using the resin described in Patent Document 1 described above for pigment dispersion is excellent in adhesive strength and boil resistance for printing a plastic film for packaging, but is a toluene-containing solvent-based ink and has a large environmental load. At the same time, it is inferior in printability, so further improvement is required. Further, the technique described in Patent Document 2 did not have a sufficient degree of biomass as an ink.

In contrast to the above, the present inventors have exhibited excellent adhesion performance to various plastic substrates, particularly biomass plastic substrates, and also have excellent dispersibility of pigments contained in high concentrations. , Proposes a polyurethane resin containing a high amount of biomass, which is useful as a binder (varnish) for printing ink having printability (see Patent Document 3). According to this technology, by using biopolyurethane resin as a varnish for printing ink, the biomass degree, which is the "biomass mark" certification standard, is 10% by mass or more, in the field of environmental conservation requirements from the viewpoint of carbon neutrality. A very useful printing ink can be provided.

Specifically, when the above-mentioned biopolyurethane resin is used as a varnish for gravure ink, for example, it is compared with other bio-based gravure inks and compared with conventional non-bio-based gravure inks. It is characterized by its excellent compatibility with ink. Therefore, there is a practical merit that troubles can be effectively suppressed when the bio-based gravure ink and the non-bio-based gravure ink described in Patent Document 3 are mixed / mixed. Further, by using the biopolyurethane resin described in Patent Document 3 for the varnish for printing ink, it becomes possible to provide a non-toluene solvent-based or non-toluene non-MEK solvent-based printing ink.

Japanese Unexamined Patent Publication No. 2-189375 Japanese Patent Application Laid-Open No. 2003-41175 JP-A-2019-172977

However, although the biopolyurethane resin described in Patent Document 3 developed by the present inventors has the above-mentioned excellent merits, it has been found that there are the following problems in practical use. That is, when the biopolyurethane resin is used as a varnish for printing ink, it has been found that the pot life and heat resistance (hot peel strength) when a hardener (hardener) is added are not sufficient depending on the application. On the other hand, in designing a new resin, it is required to realize the new property without impairing the excellent property obtained by the biopolyurethane resin described in Patent Document 3.

Specifically, the biopolyurethane resin proposed above has a feature of being extremely excellent in compatibility with non-biogravure inks when used as a varnish for printing inks, as compared with conventional inks. However, it is required that this point is maintained and that the ink has the following characteristics. The biopolyurethane resin proposed above is a solution of a polyurethane resin having an active amino group at the terminal of each molecule, for example, a linear polyurethane resin having an amino terminal group, but the present inventors have put it into practical use. We found that there are the following technical issues in the study for the conversion. Part of the terminal active amino group is replaced with an alkyl group for the purpose of suppressing the increase in the viscosity of the compounding solution that affects the pot life, which occurs when hardener (polyisocyanate component) is added to the ink for the purpose of increasing heat resistance. When the treated resin solution is used, a technical problem has been found that the hot peel strength is weak in a film obtained by laminating a printed matter printed with printing ink, and sufficient heat resistance cannot be realized.

Therefore, an object of the present invention is to maintain the characteristics obtained by the biopolyurethane resin described in Patent Document 3, further to suppress the problem of thickening of the compounding liquid when a hardener is added to the printing ink, and at the same time to suppress heat resistance. It is an object of the present invention to obtain a biopolyurethane resin having excellent properties (hot peel strength) and suitable for a varnish for printing ink. An object of the present invention is to realize a biopolyurethane resin having such characteristics, and by applying the resin to a varnish for printing ink, the obtained printing ink exhibits excellent effects even in various usage forms, and is more practical. The purpose is to enable the provision of excellent printing inks.

The above object is achieved by the following invention. That is, the present invention provides a biopolyurethane resin having the following constitution.
[1] The total amount of biological components in the polymerization component is 35% by mass or more, and the polymerization component includes a polyol component (A), an isocyanate component (B), and a polyamine component (C). It is a biopolyurethane resin that has
Further, the polymerization component contains a specific monoamine component (D) having one active amino group having an active amino group active hydrogen and another active hydrogen group, and is a terminal amino group of a terminal active amino group type polyurethane resin. It has a polyurethane polyurea structure in which a part of is replaced with another active hydrogen group.
A biopolyurethane resin characterized in that the average number of amino groups per molecule of the resin is 1.00 or more and 1.90 or less.

Preferred forms of the above-mentioned biopolyurethane resin include those having the following configurations.
[2] The specific monoamine component (D) contains an amino alcohol selected from monoethanolamine, diethanolamine, monopropanolamine, monoisopropanolamine, diisopropanolamine and 1-amino-2,3-propanediol [1]. ] The biopolyurethane resin described in.
[3] The above-mentioned [1] or [2], wherein the amino group concentration at the terminal is 15 to 100 μe equivalent per 1 g of the resin, and the other active hydrogen group concentration is 2 to 50 μe equivalent per 1 g of the resin. Biopolyurethane resin.
[4] The biopolyurethane resin according to any one of the above [1] to [3], wherein the average number of amino groups per molecule of the resin is 1.3 or more and 1.8 or less.
[5] The biopolyurethane resin according to any one of the above [1] to [4], wherein the other active hydrogen group is either a hydroxyl group or a mercapto group.
[6] The biopolyurethane resin according to any one of the above [1] to [5], wherein the polyamine component (C) contains isophorone diamine.

[7] The polyol component (A) is a polyfunctional alcohol component and a polyfunctional alcohol component containing a diol component (a) containing a biological component and a dicarboxylic acid component (b) containing a biological component as raw materials. It is a biopolyester polyol that is a polymer with a functional carboxylic acid component.
The diol component (a) is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,10-decanediol and dimerdiol derived from living organisms. The biopolyurethane resin according to any one of the above [1] to [6], which comprises at least one of the above.
[8] The dicarboxylic acid component (b) contains succinic acid derived from a living body and another dicarboxylic acid, and the molar ratio thereof is succinic acid derived from a living body / other dicarboxylic acid 98/2 to 5/95. The biopolyurethane resin according to the above [7].
[9] The biopolyurethane resin according to the above [8], wherein the other dicarboxylic acid is at least one of sebacic acid and dimer acid derived from an organism.

The present invention provides the following biourethane resin solution as another embodiment.
[10] A biopolyurethane resin solution comprising the biopolyurethane resin according to any one of the above [1] to [9] and an organic solvent.
Preferred forms of the biourethane resin solution of the present invention include the following configurations.
[11] The biopolyurethane resin solution according to the above [10], wherein the organic solvent does not contain toluene or contains neither toluene nor methyl ethyl ketone.

As another embodiment, the present invention provides the following method for producing a biourethane resin solution.
[12] The production method for obtaining the biopolyurethane resin according to any one of the above [1] to [9].
The polyol component (A) and the isocyanate component (B) are reacted to obtain a terminal isocyanate type urethane prepolymer, and the terminal isocyanate type prepolymer, the polyamine component (C), and the active amino having an active amino group active hydrogen are obtained. By reacting the specific monoamine component (D) having one group with another active hydrogen group, a part of the terminal amino group of the terminal active amino group type polyurethane resin was replaced with another active hydrogen group. A method for producing a biopolyurethane resin, which comprises obtaining a polyurethane polyurea resin having a structure having an average amino group number of 1.00 or more and 1.90 or less per molecule of the resin.

The present invention provides the following printing inks as another embodiment.
[13] In a printing ink containing a pigment and a varnish for printing ink, the ratio of the biological component to the solid content of the ink as the varnish for printing ink is 10% by mass or more, and the above [1] ] To [9], or the printing ink comprising the biopolyurethane resin solution according to the above [10] or [11].

Preferred forms of the above-mentioned printing ink include those having the following configurations.
[14] The printing ink according to the above [13], which further comprises a hardener containing an isocyanate compound.
[15] The printing ink according to the above [13] or [14], which is used for any of gravure printing, flexographic printing, screen printing, offset printing, and inkjet printing.
[16] The printing ink according to the above [13] to [15], which is used for printing on any of film packaging, paper packaging, building materials and decorative paper.

According to the present invention, the characteristics obtained by the biopolyurethane resin are maintained, the problem of thickening of the compounding liquid when the hardener is added to the printing ink is suppressed, and at the same time, heat resistance (hot peel strength) is suppressed. It is realized that a biopolyurethane resin having excellent properties and suitable for a varnish for printing ink can be obtained. According to the present invention, by realizing a biopolyurethane resin having such characteristics and applying it to a varnish for printing ink, the obtained printing ink exhibits excellent effects even in various usage forms, which is more practical. It is possible to provide excellent printing inks.

Next, the present invention will be described in more detail with reference to preferred embodiments for carrying out the invention. The present inventors have heat resistance, which is generated when the above-mentioned biopolyurethane resin solution is applied to a varnish for printing ink, and which is generated when the increase in viscosity of the compounding liquid when a hardener is added to the ink is suppressed. We enthusiastically investigated the cause of insufficient (hot peel strength) and the means to solve this problem. First, regarding the above causes, the present inventors have a molecular network structure formed by the reaction between the polyurethane resin and Hardener when a part of the terminal amino group of the terminal active amino group type polyurethane resin is replaced with an alkyl group. It was considered that the number of defects increased and the hot peel strength became weaker as a result.

Therefore, unless a treatment is performed in which a part of the terminal amino group is reacted with a monoisocyanate component to replace it with an alkyl group, defects in the molecular network structure are reduced and the hot peel strength is also improved. However, this treatment is unavoidable when it is necessary to add a hardener, and if the treatment is not performed, the problem of thickening of the ink will occur, so that it cannot be used for the varnish for printing ink for this application. .. Therefore, in order to further expand the range of use of the conventional biopolyurethane resin solution developed by the present inventors, it is required to achieve both the viscosity stability of the ink compound liquid to which the hardener is added and the hot peel strength. Will be done.

As a result of diligent studies on the above-mentioned technical problems, the present inventors have obtained a specific monoamine component (D) (D) having a biopolyurethane resin having one active amino group having active hydrogen and another active hydrogen group. Hereinafter, by using (hereinafter, also simply referred to as “specific monoamine component (D)”) as a polymerization component, a part of the terminal amino group of the terminal active amino group type polyurethane resin can be used as another active hydrogen group such as a hydroxyl group. The present invention has been made by finding that the above-mentioned technical problems can be solved by modifying the structure to have a polyurethane polyurea structure replaced with. That is, the biopolyurethane resin of the present invention in which the total amount of biological components in the polymerized components is 35% by mass or more is characterized by the following points. The biopolyurethane resin of the present invention uses a polyol component (A), an isocyanate component (B), and a polyamine component (C) as polymerization components, and further has a structure specified in the present invention such as amino alcohol. Each resin molecule has a polyurethane polyurea structure in which a part of the terminal amino group is replaced with another active hydrogen group such as a hydroxyl group, which is obtained by using the "specific monoamine component (D)" having. The average number of amino groups (APM value) of the above is 1.00 or more and 1.90 or less.

The "other active hydrogen group" that replaces a part of the terminal amino group defined in the present invention is an isocyanate group and a temperature of 40 ° C. or less within a few days in a state of being at the end of the polyurethane resin as a component of the ink. It is preferable that the functional group is capable of generally reacting and has a lower reaction rate than the amino group. Typical examples include hydroxyl groups and mercapto groups. Hereinafter, the biopolyurethane resin of the present invention having a structure in which a part of the terminal amino group is replaced with another active hydrogen group in a specific amount in the terminal active amino group type polyurethane resin which characterizes the present invention is specified. A case where an amino alcohol component is used as a typical example of the monoamine component (D), that is, a case where another active hydrogen group is a hydroxyl group will be described as an example.

The "APM value" defined in the present invention is an index showing to what extent the amino group at the terminal of the polyurethane resin is replaced with the amino alcohol component. Then, according to the study by the present inventors, in order to realize the effect of the present invention and to make the biopolyurethane resin usable as a varnish for printing ink without causing the above-mentioned problems, APM The value needs to be 1.00 or more and 1.90 or less. Further, in order to obtain a more suitable biopolyurethane resin, those having an APM value in the range of 1.3 to 1.8 are preferable. Particularly preferably, it may be designed so that the APM value is in the range of 1.5 to 1.8.

Here, the terminal amino group concentration in the polyurethane resin useful as a varnish for printing ink is 15 μe equivalent to 100 μe equivalent per 1 g of the resin, and this point is the same in the resin of the present invention and is not different from the conventional one. According to the studies by the present inventors, when the biopolyurethane resin of the present invention is used as a varnish for printing ink, the terminal hydroxyl group concentration of the polyurethane resin, that is, the concentration of other active hydrogen groups at the ends is 2μ equivalent per 1 g of the resin. It is preferably ~ 50μ equivalent.

A technique for changing a part of the terminal amino group of the polyurethane resin of the varnish for printing ink to a group other than the amino group by using a monoamine component, a monoisocyanate component, or the like is conventionally known. That is, a monoamine component, a monoisocyanate component, or the like is used as a reaction terminator or the like of the polyurethane resin, and as a result, a part of the terminal amino group of the polyurethane resin is changed to an alkyl group or the like. However, the utility brought about by changing a part of the terminal amino group to a non-amino group, for example, an alkyl group or the like by using a monoamine component or a monoisocyanate component has not been clarified so far. In particular, the utility brought about by changing to an active hydrogen group such as a hydroxyl group has not been clarified. Of course, as specified in the present invention, a part of the amino group at the end of the polyurethane resin is replaced with an amino alcohol component having an active hydrogen group such as a hydroxyl group in a specific range, and further, such a structure. The useful effects of this configuration have not been clarified.

Here, the method for replacing the specific ratio of the terminal amino group of the polyurethane resin required for obtaining the biopolyurethane resin of the present invention with a hydroxyl group is not particularly limited, and a conventional production method can be applied. For example, the following manufacturing method can be mentioned.
(1) The biopolyol component and the isocyanate component are reacted to obtain a terminal isocyanate type prepolymer.
(2) Using a terminal isocyanate type prepolymer, a polyamine component, and an amino alcohol component for introducing a hydroxyl group at the terminal, a terminal hydroxyl group type polyurethane polyurea resin in which a part of the terminal amino group is replaced with a hydroxyl group is obtained. ..

As a specific synthesis method, for example, a mixture of a polyamine component and an amino alcohol component is added to the prepolymer obtained in the step (1), or a chain is extended with the polyamine component and then the amino alcohol component is reacted. , It can be obtained by a method such as reacting the amino alcohol component and then extending the chain with the polyamine component. In the synthesis, a reaction accelerator, a reaction retarder, a reaction terminator and the like can be appropriately used.

The "specific monoamine component (D)" having one active amino group having an active hydrogen and another active hydrogen group constituting the present invention is not particularly limited, but is a compound listed below. Can be used. Specifically, each molecule has one active amino group having active hydrogen, such as monoethanolamine, diethanolamine, monopropanolamine, monoisopropanolamine, diisopropanolamine and 1-amino-2,3-propanediol. Further, an amino alcohol having a hydroxyl group as another active hydrogen group is particularly preferable. Further, mercaptoamines having one active amino group per molecule such as cysteamine and further having a mercapto group as another active hydrogen group can also be preferably used. In this specification, amino alcohol is described as a representative example as the specific monoamine component (D) defined in the present invention.

According to the studies by the present inventors, amino alcohols having only active amino groups without other active hydrogens and amino alcohols having two or more amino groups having active hydrogens per molecule are not preferable. .. However, for example, an amino alcohol having two or more amino groups having active hydrogen per molecule does not fall under the "specific monoamine component (D)" defined in the present invention, and therefore cannot be used as the component (D). However, it may be used as the polyamine component (C) constituting the present invention.

The APM value specified in the present invention is the average number of amino groups per molecule of the resin, and can be calculated by using the formulas (1) to (4) listed below, for example. The APM values obtained by using these equations have the same meaning. Therefore, an applicable calculation formula may be appropriately selected according to the attributes of the resin. For example, when the specific monoamine component (D) specified in the present invention is not used, the formula (1) cannot be applied. For the polyurethane resin solutions obtained in Examples and Comparative Examples described later, the APM values were calculated by the following methods, respectively. Specifically, PU1 to PU15 of the example and PU-C4 of the comparative example are calculated by the method of (1), and PU-C1 to PU-C3, PU-C5, and PU-C8 to PU of the comparative example are calculated. The APM value in −C14 corresponds to (2), PU-C6 of the comparative example was calculated by the method of (3), and PU-C7 was calculated by the method of (4).

(1) APM value from the amine equivalent of the resin, the hydroxyl group equivalent of the resin, and the average number of hydroxyl groups of the specific monoamine component (D) having one active amino group such as a blended amino alcohol and another active hydrogen (hydroxyl group). How to calculate APM value =
[(Amine equivalent of resin) / {(Amine equivalent of resin) + (Equivalent of hydroxyl group of resin) / (Average number of hydroxyl groups of specific monoamine component (D))}] × 2

(2) No specific monoamine component (D), monoamine component having an active amino group other than the specific monoamine component (D), monoisoisocyanate component, etc. is used, that is, all are synthesized from bifunctional components. The APM value of each resin is 2.00.

(3) Method of calculating APM value from the amine equivalent of the resin and the charged concentration of the specific monoamine component (D) APM value =
[(Amine equivalent of resin) / {(Amine equivalent of resin) + (Mixed amount g of specific monoamine component (D) / Molecular weight of specific monoamine component (D)) / (Amount charged with non-volatile component) g × 1000000}] × 2

(4) When using monoisocyanate instead of the specific monoamine component (D) to replace a part of the terminal amino group, the APM value is calculated from the amine equivalent before monoisocyanate compounding and the amine equivalent after monoisocyanate compounding. How to calculate APM value =
[(Amine equivalent after blending monoisocyanate) / (Amine equivalent before blending monoisocyanate)] × 2

Calculation method of the average number of hydroxyl groups of the amino alcohol blended as the specific monoamine component (D) used in the above (1) = The average number of hydroxyl groups of the amino alcohol =
[Σi (number of blended moles of amino alcohol component i x number of hydroxyl groups in one molecule of amino alcohol component i)] / [Σi (number of blended moles of amino alcohol component i)]

The average number of amino groups per molecule of the resin can also be obtained from the product of the number average molecular weight of the polyurethane resin and the amine equivalent. For example, in the case of a resin having a number average molecular weight of 50,000 and an amine equivalent of 30 μ, the average number of amino groups per molecule of the resin is 1.50.

The biopolyurethane resin of the present invention has a total amount of biological components in the polymerization component of 35% by mass or more, and the polymerization components include a polyol component (A), an isocyanate component (B), and a polyamine component. It is a biopolyurethane resin having (C), and further, the polymerization component contains the specific monoamine component (D) described above, and a part of the terminal amino group of the terminal active amino group type polyurethane resin is a hydroxyl group. Any material having a polyurethane polyurea structure having an APM value of 1.00 or more and 1.90 or less, which is replaced with another active hydrogen group such as 1.00 or more, may be used.

The biopolyurethane resin of the present invention is preferably synthesized, for example, by using the polyol component (A), which is a polymer obtained by polymerizing the following raw material components. That is, the above-mentioned polyol component (A) is a biopolyol component, and the raw material component includes a diol component (a) containing a biological component and a dicarboxylic acid component (b) containing a biological component. , A biopolyester polyol which is a polymer of a polyfunctional alcohol component and a polyfunctional carboxylic acid component is preferable. More specifically, for example, the diol component (a) is a biological origin, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,10-decanediol and It contains at least one selected from the group consisting of dimerdiol, and the dicarboxylic acid component (b) contains a biological succinic acid and another dicarboxylic acid, and the molar ratio thereof is the biological succinic acid /. It is preferable to use a biopolyester polyol which is a polymer obtained by polymerizing another dicarboxylic acid 98/2 to 5/95 as the polyol component (A).

Details of the diol component (a) and the dicarboxylic acid component (b) constituting the polyol component (A), and the isocyanate component (B) and the polyamine component (C) used together with the polyol component (A) are described above. It is described in the above-mentioned Document 3, and the biopolyurethane resin of the present invention can be easily obtained by using these raw material components. More specifically, the biopolyurethane resin of the present invention has a configuration in which a polyamine component (C) is used as a reaction component in addition to the polyol component (A) and the isocyanate component (B) described in Document 3. In a biopolyurethane resin having a terminal active amino group type structure, a part of the terminal amino group is replaced with another active hydrogen group such as a hydroxyl group in a specific range by using a specific monoamine component (D) for modification. It corresponds to the one with the above structure. Therefore, all the raw materials other than the specific monoamine component (D) that characterizes the present invention are described in Document 3 mentioned above, and any of these raw material components can be used in the present invention. The outline of the raw material components other than the specific monoamine component (D) used in synthesizing the biopolyurethane resin of the present invention will be described below. In the present invention, a component derived from a living organism is described as "derived from a living organism" or by adding a bio to the head of the component name to distinguish it from a normal component derived from petroleum.

[Biological diol component (a)]
The diol component (a), which is a polyfunctional alcohol component used in the synthesis of the biopolyol polyol described above, includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4, which are biological components. One or more selected from the group consisting of -butanediol, 1,10-decanediol and dimerdiol can be used. Among these, ethylene glycol, 1,2-propanediol, 1,3-propanediol and 1,4-butanediol derived from living organisms are preferable, and bio-1,2-propanediol and bio-1, 3-Propanediol is preferred. These may be used alone or in combination of two or more. When bio-1,2-propanediol or bio-1,3-propanediol is used as a raw material for synthesizing the polyester polyol used for synthesizing the biopolyurethane resin of the present invention, the above-mentioned bio-derived polyfunctionality is used. The content of these in the alcohol component is preferably 10 mol% or more, and more preferably 50 mol% or more. With this configuration, when the finally obtained polyurethane resin is applied to a varnish for printing ink to form an ink, the balance between pigment dispersibility, printability, and adhesion to a film substrate is improved.

Furthermore, when a biopolyurethane resin made of 1,2-propanediol or 1,3-propanediol derived from a living organism is applied to a varnish for printing ink for the synthesis of a biopolyester polyol, it is used first in a printing apparatus. The effect of excellent compatibility with the printing ink that has been used can be obtained. Due to the effect of excellent compatibility with the conventional petroleum-based printing ink, the printing ink using the biopolyurethane resin of the present invention is a printing device that occurs in the process of printing work and becomes a problem when the printing ink is changed. It is possible to realize the effect of reducing the work load required for cleaning the inside and replacing the ink. This effect not only reduces the labor in work, but also reduces the materials required for cleaning and ink replacement, which is extremely useful industrially. In addition, there is an advantage that troubles are less likely to occur even when mixed with other inks for adjusting the hue and it is easy to use, which is also industrially useful.

[Dicarboxylic acid component (b)]
As the dicarboxylic acid component (b), which is a polyfunctional carboxylic acid component used for synthesizing a biopolyester polyol, it is preferable to use biologically derived succinic acid. Examples of the biodicarboxylic acid component other than biosuccinic acid include glutaric acid, sebacic acid, dimer acid and the like. When biosuccinic acid derived from a living organism is used as the dicarboxylic acid component (b) and further used in combination with another dicarboxylic acid, and the biosuccinic acid is used in combination with another dicarboxylic acid, the molar ratio thereof is bio. Succinic acid / other dicarboxylic acid = 98/2 to 5/95. As the other carboxylic acid, it is preferable to use a bio-derived dicarboxylic acid as listed above in order to realize a higher biomass degree than specified in the present invention. However, a petroleum-derived dicarboxylic acid component may be contained as long as a high biomass content of 35% by mass or more and 40% by mass or more, which is the object of the present invention, can be realized. When the biopolyurethane resin of the present invention is constructed using a petroleum-derived dicarboxylic acid component, the cost of the biological material is higher than that of the petroleum-based material, so that the material cost can be reduced. ..

As described above, in the biopolyurethane resin of the present invention, for example, the dicarboxylic acid component (b) used for synthesizing the biopolyester polyol as a raw material contains a biological component and the biological component / other carboxylic acid. The molar ratio of the acid may be 98/2 to 5/95. In this case, the combination of two different types of dicarboxylic acid components includes, for example, a combination of succinic acid derived from an organism and adipic acid derived from petroleum, a combination of succinic acid derived from an organism and a dimer acid derived from an organism, and a combination derived from an organism. Examples thereof include a combination of succinic acid and biological sebacic acid.

When biodimeric acid and biosuccinic acid are used as synthetic raw materials for the biopolyester polyol constituting the present invention, the total amount of biodimeric acid and biosuccinic acid in the above-mentioned bio-derived polyfunctional carboxylic acid component is used. The content is preferably 30 mol% or more, more preferably 40 mol% or more. With this configuration, when the finally obtained polyurethane resin solution is applied to a varnish for printing ink to form an ink, the balance between pigment dispersibility, printability, and adhesion to a film substrate is improved.

[Petroleum-derived raw materials]
In order to obtain a printing ink that satisfies the "biomass mark" certification standard, which is one of the objects of the present invention, as specified in the present invention, the ratio of biological components in the polyurethane resin used for the varnish for printing ink is determined. It is necessary to make it 35% by mass or more, and further 40% by mass or more. Therefore, it is necessary that the raw material component of the biopolyol component (A) constituting the present invention contains the above-mentioned biological component at a high usage ratio. However, the raw material component of the biopolyol component (A) includes a specific component specified in the present invention, and is a petroleum-derived raw material as listed below to the extent that it does not interfere with the intended purpose of the present invention. Can be used together.

Examples of the petroleum-derived polyfunctional alcohol that can be used in the present invention include compounds having two or more, preferably 2 to 8 hydroxyl groups in one molecule. Specifically, for example, petroleum-derived ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, and dipropylene. Glycol, 1,6-hexanediol, neopentyl glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl-1,5-pentane Diol and the like can be used in combination as long as they do not interfere with the intended purpose of the present invention. These may be used alone or in combination of two or more.

Examples of the petroleum-derived polyfunctional carboxylic acid that can be used in the present invention include succinic acid, adipic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic acid, trimellitic acid, and pyromellitic acid. It can be used in combination as long as it does not interfere with the intended purpose of the present invention.

In the biopolyurethane resin of the present invention, if the biomass degree of the finally obtained resin specified in the present invention can be achieved, a polyester polyol derived from petroleum, a polyether polyol derived from petroleum, or the like is used in combination as the polyol component (A). It is also possible. Specifically, for example, petroleum-derived polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxytetramethylene glycol, polycaprolactone diol, polymethylvalerolactone diol, polycarbonate diol, and polybutadiene diol. Etc. can be used as appropriate.

The present invention finally aims to develop a varnish material for printing inks having a high degree of biomass, which can provide high-performance printing inks of non-toluene solvent type or non-toluene non-MEK solvent type. .. The polyester polyol for polyurethane resin, which is generally considered to be useful as a vehicle for conventional non-toluene solvent-based and non-toluene non-MEK-based inks, is 2-methyl-1,3, which is a component derived from petroleum. -Adipate polyesters such as propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol are known. Therefore, in particular, the biopolyurethane resin of the present invention having a structure obtained by using these adipate polyesters and copolymerizing them with the biopolyol component described above is a non-toluene solvent-based resin or a non-toluene non. It becomes possible to realize MEK-based printing ink. Further, it is useful as a material for biomass printing ink, which makes it possible to adjust the degree of biomass from the viewpoint of cost in consideration of the practical problem that the raw material for biocomponents is generally expensive.

[Isocyanate component (B)]
As the isocyanate component (B) constituting the biopolyurethane resin of the present invention, any known compound derived from diisocyanate can be used. Specifically, hexamethylene diisocyanate, butane-1,4-diisisethylene, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate. And other aliphatic diisocyanis, isophoron diisocyanis, cyclohexane-1,4-diisocyanis, lysine diisocyanate, dicyclohexamethylene-4,4'-diisocyanis, 1,3-bis (isocyanismethyl) cyclohexane, methylcyclohexane diisocyanate, 4,4' Examples thereof include alicyclic diisocyanates such as -dicyclohexamethylene diisocyanate, isopropyridene dicyclohexyl-4,4'-diisocyanate and norbornan diisocyanate. Further, aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate can be mentioned. From the comprehensive viewpoint of reactivity, physical properties, etc., isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate are preferable. These can be used alone or in combination of two or more.

Further, in the biopolyurethane resin of the present invention, in addition to the above, it is also preferable to use a biologically derived diisocyanate as the isocyanate component (B) in order to achieve the high degree of biomass specified in the present invention. The diisocyanate derived from a living organism is converted into a terminal amino group by acid amidating and reducing a dihydric carboxylic acid derived from the living organism, and further by converting the amino group into an isocyanate group by a phosgene method, a urea method, or the like. can get.

[Polyamine component (C)]
The polyamine (C) used for synthesizing the biopolyurethane resin of the present invention is not particularly limited, but it is preferable to use a diamine having two amino groups capable of reacting with the isocyanate group as described below. As the diamine, conventionally known aliphatic, alicyclic and aromatic diamines can be used. For example, ethylenediamine, propylenediamine, butylene diamine, hexamethylenediamine, trimethylhexamethylenediamine, isophoronediamine, cyclohexyldiamine, piperazine, 2-methylpiperazin, phenylenediamine, tolylenediamine, xylenediamine, 1,3-cyclohexyldiamine, 4 , 4'-Diaminodicyclohexylamine, m-xylylene diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylpropylenediamine, di-2-hydroxypropylethylenediamine, polyoxyalkylenediamine and their like. Examples thereof include diamines such as hydrogenated products or mixtures thereof. In addition, diamines composed of biological components such as 1,5-pentanediamine derived from cellulose, 1,10-decanediamine derived from plant-based fats and oils, and dimerdiamine are also used as long as they do not interfere with the intended purpose of the present invention. be able to.

Further, if necessary, monoamines as a reaction terminator can be used in combination with the above-mentioned polyamines. Examples of the monoamines used in this case include mono-n-butylamine and di-n-butylamine. When using a reaction terminator in combination, it is necessary to consider the effect on the APM value specified in the present invention.

[Organic solvent]
When the biopolyurethane resin of the present invention is used as a varnish for printing ink, for example, it is preferably in the form of a solution containing an organic solvent. That is, the organic solvent is used in the synthesis of the resin and in the dilution for adjusting the viscosity and the concentration. In the case of a solution, the biopolyurethane resin of the present invention is well dissolved in the organic solvent used, and the organic solvent does not contain toluene or contains neither toluene nor MEK. Is preferable. The organic solvent to be used may be any one that dissolves the biopolyurethane resin of the present invention, and any known organic solvent can be used. Further, from the viewpoint of dealing with environmental problems such as odor and safety, it is desirable that the form does not contain toluene or does not contain toluene and MEK. In the case of non-toluene type, for example, a mixed solvent of ester solvent / alcohol solvent / ketone solvent is preferably used, and in the case of non-toluene non-MEK type, ester solvent / alcohol solvent. A mixed solvent is preferably used.

Examples of the ester solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate and the like. A particularly suitable solvent in the present invention is ethyl acetate.

Examples of the alcohol-based solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tertiary butyl alcohol and the like, and glycol monoalkyl ethers such as ethylene glycol monomethyl ether and the like. A particularly suitable solvent in the present invention is isopropyl alcohol.

Examples of the ketone solvent include acetone, methyl ethyl ketone (MEK), diisobutyl ketone and the like. A particularly suitable solvent is MEK. When emphasizing high-speed printing suitability, it is advantageous to use MEK. On the other hand, when the target composition is a non-toluene non-MEK-based printing ink in consideration of air pollutants typified by harmful air pollutant (HAPS) regulations, it is manufactured without using toluene and MEK.

When the biopolyurethane resin of the present invention is in the form of a solution, a biologically-derived organic solvent is contained as an organic solvent within a range that does not affect the performance of the printing ink when used in, for example, a varnish for printing ink. Can be done. For example, if a biological solvent (for example, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, ethyl alcohol) is used as a part of the organic solvent used in the synthesis of the biopolyurethane resin, the constituent components of the resin are used. Not only that, the solvent component is also a material that takes into consideration the reduction of CO ₂ emissions.

[Polyurethane resin solution]
The biopolyurethane resin of the present invention has a urethane urea bond in its structure, achieving a high degree of biomass by using the polyamine component (C) and the specific monoamine component (D) mentioned above as reaction components. The polyurethane resin is a polyester-based polyurethane resin in which a part of the terminal amino group of the terminal active amino group type polyurethane resin is replaced with another active hydrogen group such as a hydroxyl group in a specific range. More specifically, the biopolyurethane resin of the present invention is characterized in that the average number of amino groups (APM value) per molecule of the resin is 1.00 or more and 1.90 or less. In a preferred embodiment, the concentration of the active amino group is 15 to 100 μe equivalent per 1 g of the resin, and the terminal hydroxyl group concentration is 2 to 50 μe equivalent per 1 g of the resin.

An object of the present invention is to find a liquid resin material useful for a varnish for printing ink, and for that purpose, an ester solvent, an alcohol solvent and / or a ketone solvent of a biopolyurethane resin having the above structural characteristics is used. An example is to use a resin solution composed of a solvent. With this configuration, the biological component suitable for pigment dispersion has a high biomass content of 35% by mass or more, and further 40% by mass or more, in the resin solid content. It becomes a biomass resin solution that has. When the polyurethane resin solution of the present invention having such a structure is used as a pigment dispersion varnish for ink applications, it has a high degree of biomass, pigment dispersion stability, adhesion to a base film to be printed, printability, and the like. It becomes possible to realize excellent printing ink.

[Manufacturing method of polyurethane resin solution]
The biopolyurethane resin solution of the present invention having the above-mentioned structural characteristics synthesized by using a biological raw material can be produced as follows. For example, the biopolyol made of the raw material described above, the polyol component (A) containing a petroleum-derived polyol, a short-chain diol, and the like, and the isocyanate (B) component are reacted with these materials to react the isocyanate (B) component to both ends of the isocyanate urethane. Obtain a prepolymer. Then, the polyamine component (C) is reacted with the specific monoamine component (D) to carry out a chain extension reaction, a reaction in which a part of the terminal amino group of the terminal active amino group type polyurethane resin is replaced with a hydroxyl group. Can be obtained by letting. The organic solvent described above may be used as the solution of the component (C) and the component (D). When it is necessary to adjust the concentration of the active amino group at the end of the polyurethane resin, monoamines as a terminator can be appropriately used, or a monoisocyanate compound can be used. Further, in the production of the above-mentioned double-ended isocyanate urethane prepolymer, a reaction catalyst composed of a metal catalyst or an amine salt can be used, if necessary.

<Printing ink>
The printing ink of the present invention contains a pigment and a varnish for printing ink, and the biopolyurethane resin solution of the present invention is contained in an amount such that the ratio of biological components in the ink solid content is 10% by mass or more. It is characterized by being used as a varnish for printing ink. Specifically, the biomass resin solution of the present invention obtained as described above, the pigment, and the organic solvent for dilution are dispersed using various known dispersers to obtain biological components. A printing ink that achieves a high degree of biomass can be obtained. As the organic solvent for dilution, as described above, an ester solvent, an alcohol solvent and / or a ketone solvent, and more preferably, a toluene-free solvent or a toluene-free MEK-free solvent is used. Is preferable. Further, the printing ink of the present invention includes, if necessary, a hardener containing an isocyanate compound, a pigment dispersant, an antiblocking agent, an antifoaming agent, a leveling agent, a coupling agent such as a silane type or a titanate type, a plasticizer, water, and the like. It is also possible to add a slow-drying solvent for drying control, a viscosity stabilizer such as an organic acid, an ultraviolet absorber, an antioxidant and the like. According to the present invention, the biopolyurethane resin of the present invention achieves both the viscosity stability of the ink compounding liquid and the hot peel strength, which are particularly required in the configuration of a printing ink to which a hardener containing an isocyanate compound is added. This can be achieved by using the solution as an ink varnish.

Further, nitrified cotton, chlorinated polyethylene, chlorinated polypropylene, vinyl acetate copolymer resin, maleic acid resin, polyvinyl butyral resin, fibrous resin and the like can be used in combination with the printing ink.

The printing ink of the present invention prepared as described above can be applied to various printing methods. Specifically, it is used for any one of gravure printing, flexographic printing, screen printing, offset printing or inkjet printing. Especially suitable for gravure printing.

Further, the printing ink of the present invention having the above-mentioned structure can be applied to various substrates, and for example, good printing can be performed on various biomass plastic films made of plant-derived materials, plant-derived paper, and the like. In particular, it can be widely used for various purposes such as film packaging, paper packaging, building materials or decorative paper for food packaging.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, "part" or "%" in the text is based on mass unless otherwise specified.

[Preparation of polyurethane resin solution]
(Manufacturing Example 1)
A polyester polyol was prepared as follows. As a polyfunctional carboxylic acid component (hereinafter referred to as a dicarboxylic acid component), dimer acid composed of a biological component (dimer purity 98%) / succinic acid composed of a biological component = 90/10 (molar ratio) is used and polyfunctional. As an alcohol component (hereinafter referred to as a diol component), 1,3-propanediol composed of a biological component was used. Then, these components were polymerized using an appropriate amount having a target molecular weight, and shown in Table 1-1, the hydroxyl value was 37.3 mgKOH / g, the acid value was 0.3 mgKOH / g, and the number average. A polyester diol PE (1) having a molecular weight of 3000 and composed of 100% biological components was obtained.

(Manufacturing Examples 2 to 16)
Polyester polyol PE (2) to PE (16) was prepared respectively. In addition, Table 2 shows the abbreviations in the table of the synthetic raw materials used.

(Example 1)
A polyurethane resin solution was prepared using the polyol component (A) obtained in Production Example 1. In the reaction vessel, 500 parts of the polyester diol PE (1) obtained in Production Example 1 and 66.4 parts of isophorone diisocyanate (hereinafter abbreviated as IPDI) which is an organic diisocyanate as an isocyanate component (B) are charged, and a nitrogen stream is charged. Under the reaction, the reaction was carried out at 100 ° C. for 5 hours to obtain a urethane prepolymer having an NCO group content of 1.87%. The obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate as a diluting solvent to prepare a urethane prepolymer solution (1) having a non-volatile content of 75%.

Next, as the polyamine component (C), 23.2 parts of isophorone diamine (hereinafter abbreviated as IPDA), 0.168 parts of monoethanolamine (hereinafter abbreviated as MEA) which is a specific monoamine component (D), and acetic acid. A mixture (diamine solution) of 980.9 parts of ethyl and 206.5 parts of isopropyl alcohol (hereinafter abbreviated as IPA) was mixed, and the previously obtained urethane prepolymer solution (1) was added dropwise with stirring. The reaction was carried out at 40 ° C. for 1 hour. As a result, a polyurethane resin solution PU1 of this example having a non-volatile content (solid content) of 30% and a viscosity of 1120 mPa · s (25 ° C.) and a biological component of 84.8% in the resin solid content was obtained. The terminal amino group concentration of PU1 is 40.2 μe equivalent per 1 g of resin (hereinafter abbreviated as amino group equivalent), and the terminal hydroxyl group concentration is 4.5 μ equivalent per 1 g of resin (hereinafter abbreviated as hydroxyl group equivalent). The APM value indicating the average number of amino groups in one molecule of the resin calculated from these was 1.80. Table 3-1 shows the composition of the synthetic raw material component and the properties of the resin of the polyurethane resin solution PU1 obtained above.

(Examples 2 to 15)
Using the polyester polyols PE (1) to PE (10) obtained in the previous production example, each synthetic raw material component shown in Table 3-1 and Table 3-2 (may be collectively referred to as Table 3) is used. , Urethane prepolymer solutions were prepared in the same manner as in Example 1 except that the amounts used in Table 3 were used. Next, the polyurethane resin solutions PU2 to PU13 of each example were used in the same manner as in Example 1 except that the synthetic raw material components shown in Tables 3-1 and 3-2 were used in the amounts shown in Table 3, respectively. Got In addition, Table 3 shows the properties of the polyurethane resin solution obtained above. In addition, Table 6 summarizes the names of the isocyanate compounds and amine components described by abbreviations in Tables 3 to 5 and the number of isocyanate groups, amino groups and hydroxyl groups thereof.

(Example 14)
In this example, a polyurethane resin solution PU14 was prepared by using two kinds of the polyols obtained in the production example in combination. 250 parts of the polyester diol PE (2) obtained in Production Example 2, 250 parts of the polyester diol PE (11) obtained in Production Example 11, and 78.5 parts of IPDI were charged in the reaction vessel under a nitrogen stream. The reaction was carried out at 100 ° C. for 5 hours to obtain a urethane prepolymer having an NCO group content of 1.93%. The obtained urethane prepolymer was dissolved in 192.8 parts of ethyl acetate as an organic solvent for dilution to obtain a urethane prepolymer solution (14) having a non-volatile content of 75%.

Next, a mixture (diamine solution) of 23.7 parts of IPDA, 0.347 parts of MEA, 1002.1 parts of ethyl acetate, and 210.9 parts of IPA was mixed and obtained first with stirring. The urethane prepolymer solution (14) was added dropwise and reacted at 40 ° C. for 1 hour. As a result, a polyurethane resin solution PU14 of this example having a non-volatile content (solid content) of 30% and a viscosity of 1140 mPa · s (25 ° C.) and having 41.5% of biological components in the resin solid content was obtained. The amino group equivalent of PU14 was 31.5 μe equivalent, the hydroxyl group equivalent was 10.0 μe equivalent, and the APM value indicating the average number of amino groups in one molecule of the resin calculated from this was 1.52. Table 4 shows the composition of the synthetic raw material component and the properties of the resin of PU14 obtained above.

(Example 15)
Non-volatile in the same manner as in Example 14, except that PE (2) and PE (11) used in Example 14 were PE (10) and PE (12) obtained in Production Example 10 and Production Example 12. A polyurethane resin solution PU (15) of this example having a content (solid content) of 30% and a viscosity of 1170 mPa · s (25 ° C.) and a biological component of 49.9% in the resin solid content was obtained. The obtained PU (15) has an amino group equivalent of 29.9 μe and a hydroxyl group equivalent of 4.5 μe, and the APM value indicating the average number of amino groups in one molecule of the resin calculated from this is 1.74. Met. Table 4 shows the composition of the synthetic raw material component and the properties of the resin of PU15 obtained above.

(Comparative Example 1)
The polyester polyols PE (1) to (4), PE (10), PE (11), PE (13) to PE (16) obtained in the production example were used, and Tables 5-1 and 5-2 (collectively) were used. The synthetic raw material components as shown in Table 5) were used in the amounts described, and after the amine compound and the prepolymer solution were reacted with PU-C7, DDI was added and reacted for 30 minutes. Except for the above, urethane prepolymer solutions were prepared in the same procedure as in Example 1. Next, polyurethane resin solutions PU-C1 to PU-C14 of Comparative Examples were obtained in the same manner as in Example 1 except that the synthetic raw materials shown in Table 5 were used in the amounts described. In addition, Table 5 shows the composition and properties of the polyurethane resin solution obtained above.

<Evaluation>
The performance evaluation of each polyurethane resin solution of Examples and Comparative Examples was carried out by preparing a printing ink containing each resin solution as follows and using the obtained printing ink.

[Preparation of printing ink: Examples 1 to 15 and Comparative Examples 1 to 14]
Using 40 parts each of the polyurethane resin solutions of Examples and Comparative Examples, the printing inks of Examples and Comparative Examples were prepared as follows. Specifically, a mixture consisting of 30 parts of titanium oxide white as a pigment, 40 parts of each polyurethane resin solution, 15 parts of n-propyl acetate and 15 parts of isopropyl alcohol is kneaded with a paint shaker for 1 hour to white. Ink was prepared. Further, the viscosity of the obtained white ink was adjusted to # 3 Zahn cup for 18 seconds with a mixed solvent of npropyl acetate / ethyl acetate / IPA for dilution (mass ratio 40/40/20), and the examples and comparisons were made. The example printing inks were obtained respectively.

(Evaluation method and evaluation criteria for printing ink)
Using the printing inks of Examples and Comparative Examples prepared above, evaluations were made according to the following test methods and criteria, and the results are summarized in Table 7 (Tables 7-1 to 7-4).

(1) Biomass component amount The content (mass%) of the biomass component in the biomass urethane resin in the solid content of each printing ink of Examples and Comparative Examples was calculated and calculated, and evaluated according to the following criteria.
(Evaluation criteria)
◯: The biomass component content is 10% or more.
X: Biomass component content is less than 10%.

(2) Compatibility In order to evaluate the compatibility with the standard printing ink derived from petroleum, the standard ink was prepared for evaluation as follows. First, 500 parts of polyester diol PE (4) having 100% petroleum-derived components and 66.4 parts of IPDI were charged in a reaction vessel and reacted at 100 ° C. for 5 hours under a nitrogen stream to have an NCO group content of 1. A .87% urethane prepolymer was obtained. Next, the obtained urethane prepolymer was dissolved in 188.8 parts of ethyl acetate as an organic solvent for dilution to obtain a urethane prepolymer solution having a non-volatile content of 75%. Next, a mixture (diamine solution) of 23.6 parts of IPDA, 981.4 parts of ethyl acetate, and 206.5 parts of IPA was mixed, and the urethane prepolymer solution obtained above was 755.2 while stirring. The parts were dropped and reacted at 40 ° C. for 1 hour. As a result, a polyurethane resin solution having a non-volatile content of 30%, a viscosity of 1150 mPa · s (25 ° C.), a terminal amino group concentration of 42.8 μe equivalent per 1 g of the resin, and no biological component in the resin solid content was obtained. ..

Then, a mixture having a composition of 40 parts of the obtained polyurethane resin solution, 30 parts of titanium oxide white, 15 parts of n-propyl acetate and 15 parts of IPA was kneaded with a paint shaker for 1 hour to obtain white ink. Prepared. Further, the viscosity of the obtained white ink is adjusted to # 3 Zahn cup for 18 seconds with a mixed solvent of npropyl acetate / ethyl acetate / IPA for dilution (mass ratio 40/40/20) for compatibility evaluation. Standard printing ink (raw material is 100% derived from petroleum) was obtained.

Take 100 copies of the standard printing ink for compatibility evaluation prepared above, take 100 copies of the printing inks of Examples and Comparative Examples, and pour them into the standard printing ink made of the above petroleum-derived raw materials. Was visually observed, and the compatibility between the standard printing ink and the printing ink to be evaluated was evaluated according to the following criteria.

(Evaluation criteria)
⊚: It became uniform just by mixing.
◯: It became non-uniform when mixed, but became uniform when stirred.
X: Not uniform even after stirring.

(3) Pigment dispersibility A small amount of each of the printing inks of Examples and Comparative Examples was dropped on a white colored paper with a black belt, and the dropped ink was spread with a metal spatula to improve the uniformity and color development of the pigment dispersion. It was visually observed and evaluated according to the following criteria.

(Evaluation criteria)
⊚: Pigment dispersion is uniform and color development is good.
◯: Pigment dispersion is almost uniform, and color development is almost good.
Δ: The pigment dispersion is slightly non-uniform, and the color development is slightly poor.
X: The pigment dispersion is non-uniform, and the color development is clearly inferior.

(4) Printability Set each of the printing inks of the examples and comparative examples in a gravure printing machine equipped with a gravure plate having a plate depth of 35 μm, and rotate the printing ink in a 25 ° C environment for 30 minutes while applying the doctor blade to the plate. The change in color development in the printed matter before and after the printing was visually observed and evaluated according to the following criteria. The substrate of the printed matter was a 12 μm-thick biaxially stretched biomass PET treated with corona discharge.

(Evaluation criteria)
◯: There was no difference in the color development of the gravure printing machine before and after the rotation for 30 minutes.
Δ: The color development of the print after the gravure printing machine has rotated for 30 minutes is slightly inferior to that at the start of the rotation.
X: The color development of the print after the gravure printing machine has rotated for 30 minutes is clearly inferior to that at the start of the rotation.

(5) Adhesiveness (tape adhesion test)
Each of the printing inks of Examples and Comparative Examples was set in a gravure printing machine equipped with a gravure plate having a plate depth of 35 μm, and 2 each was applied to a 12 μm-thick biaxially stretched biomass PET film substrate subjected to corona discharge treatment. The printing was repeated and dried at 50 ° C. to obtain white printing films for evaluation.

Then, the adhesion of the ink of the obtained white printing film after being left for one day was evaluated by a tape adhesion test performed using cellophane tape (manufactured by Nichiban, cellophane tape (registered trademark), 24 mm). Specifically, the cellophane tape is attached to the printed surface of each white printing film, and the state of the printed surface when the cellophane tape is peeled off at a stretch at an angle of 90 degrees is visually observed, and the ink remaining on the printed surface remains. The quality of the adhesiveness of the printing ink was judged by the rate. In the tape adhesion test, if the residual ratio of the printing ink is 90% or more, it is sufficiently practical.

(6) Hardener compounding liquid Viscosity retention 100 parts of white ink obtained in Examples and Comparative Examples adjusted to 20 ° C. was mixed and diluted solvent (npropyl acetate / ethyl acetate / IPA = 40 /) adjusted to 20 ° C. After adjusting the ink viscosity to 18 seconds with Zahn Cup # 3 using 40/20), add 0.2 part of Ramic SR Hardener (isocyanate compound type, manufactured by Dainichiseika Kogyo Co., Ltd.) and use a mixer (1000 rpm) for 30 seconds. After stirring and allowing to stand for 1 minute, measure the initial viscosity with Zahn Cup # 3. After that, it is sealed in a metal container and allowed to stand in a constant temperature bath at 20 ° C., and after 1 hour, the viscosity is measured again with Zahn Cup # 3 and the viscosity change rate is measured.
(Viscosity ratio) = (Viscosity after 1 hour) / (Initial viscosity)

(Evaluation criteria)
⊚: (viscosity ratio) less than 1.5 ○: (viscosity ratio) 1.5 or more to less than 2.0 ×: (viscosity ratio) 2.0 or more

(7) Heat resistance (hot laminate strength)
(Creation of printed matter)
100 parts of the white ink obtained in Examples and Comparative Examples was adjusted to 18 seconds with Zahn Cup # 3 using a diluting solvent (MEK / ethyl acetate / IPA = 40/40/20), and then Ramic SR Hardener (Dainichiseika). A printing speed of 100 m for a 12 μm-thick biaxially stretched biomass PET film treated with corona discharge using a gravure printing machine equipped with a Helio 175 L solid plate (plate type; compressed) with 5 copies added (manufactured by Kogyo Co., Ltd.). Printing was performed once at / minute. Then, it was aged in a dryer at 40 ° C. for 24 hours to obtain printed matter of Examples and Comparative Examples.

(Dry laminating)
A polyester-based dry laminating agent (Seikabond E-263 / C-75N manufactured by Dainichiseika Kogyo Co., Ltd.) was adjusted to have a solid content of 30% using ethyl acetate, and then the printed matter surface of the previously prepared printed matter was prepared. It was applied and dried so that the applied amount after drying was 3.0 g / m ² . After that, a biaxially stretched nylon film having a thickness of 15 μm is bonded to the dry laminating agent layer to perform a dry laminating process, and further, a polyester-based dry laminating agent is applied and dried on the nylon film surface in the same manner as in the above method. An unstretched polypropylene film having a thickness of 60 μm was attached to the dry laminating agent layer to perform a dry laminating process, and the product was aged at 40 ° C. for 48 hours to obtain a laminated product.

(Measurement of hot laminate strength)
The obtained laminate was cut to a width of 15 mm and mounted on a universal tensile tester in an atmosphere of 100 ° C., and the laminate strength between the biomass PET film and the nylon film was measured.
(Evaluation criteria)
⊚: 1.0N or more ○: 0.5N or more and less than 1.0N ×: less than 0.5N

Claims (16)

A biopolyurethane having a total amount of biological components in the polymerization component of 35% by mass or more and having a polyol component (A), an isocyanate component (B), and a polyamine component (C) in the polymerization component. It ’s a resin,
Further, the polymerization component contains a specific monoamine component (D) having one active amino group having an active amino group active hydrogen and another active hydrogen group, and is a terminal amino group of a terminal active amino group type polyurethane resin. It has a polyurethane polyurea structure in which a part of is replaced with another active hydrogen group.
A biopolyurethane resin characterized in that the average number of amino groups per molecule of the resin is 1.00 or more and 1.90 or less. The first aspect of claim 1, wherein the specific monoamine component (D) contains an amino alcohol selected from monoethanolamine, diethanolamine, monopropanolamine, monoisopropanolamine, diisopropanolamine and 1-amino-2,3-propanediol. Biopolyurethane resin. The biopolyurethane resin according to claim 1 or 2, wherein the terminal amino group concentration is 15 to 100 μe equivalent per 1 g of the resin, and the other active hydrogen group concentration is 2 to 50 μe equivalent per 1 g of the resin. The biopolyurethane resin according to any one of claims 1 to 3, wherein the average number of amino groups per molecule of the resin is 1.3 or more and 1.8 or less. The biopolyurethane resin according to any one of claims 1 to 4, wherein the other active hydrogen group is either a hydroxyl group or a mercapto group. The biopolyurethane resin according to any one of claims 1 to 5, wherein the polyamine component (C) contains isophorone diamine. The polyol component (A) is a polyfunctional alcohol component and a polyfunctional carboxylic acid, which comprises a diol component (a) containing a biological component and a dicarboxylic acid component (b) containing a biological component as raw materials. It is a biopolyester polyol that is a polymer with the ingredients.
The diol component (a) is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,10-decanediol and dimerdiol derived from living organisms. The biopolyurethane resin according to any one of claims 1 to 6, which comprises at least one of the above. The claim that the dicarboxylic acid component (b) contains a biological succinic acid and another dicarboxylic acid, and the molar ratio thereof is biological succinic acid / other dicarboxylic acid 98/2 to 5/95. 7. The biopolyurethane resin according to 7. The biopolyurethane resin according to claim 8, wherein the other dicarboxylic acid is at least one of sebacic acid and dimer acid derived from an organism. A biopolyurethane resin solution comprising the biopolyurethane resin according to any one of claims 1 to 9 and an organic solvent. The biopolyurethane resin solution according to claim 10, wherein the organic solvent does not contain toluene or contains neither toluene nor methyl ethyl ketone. The production method for obtaining the biopolyurethane resin according to any one of claims 1 to 9.
The polyol component (A) and the isocyanate component (B) are reacted to obtain a terminal isocyanate type urethane prepolymer, and the terminal isocyanate type prepolymer, the polyamine component (C), and the active amino having an active amino group active hydrogen are obtained. By reacting the specific monoamine component (D) having one group with another active hydrogen group, a part of the terminal amino group of the terminal active amino group type polyurethane resin was replaced with another active hydrogen group. A method for producing a biopolyurethane resin, which comprises obtaining a polyurethane polyurea resin having a structure having an average amino group number of 1.00 or more and 1.90 or less per molecule of the resin. In the printing ink containing the pigment and the varnish for printing ink, the ratio of the biological component to the solid content of the ink as the varnish for printing ink is 10% by mass or more, according to claims 1 to 9. A printing ink comprising the biopolyurethane resin according to any one of the above or the biopolyurethane resin solution according to claim 10 or 11. The printing ink according to claim 13, further comprising a hardener containing an isocyanate compound. The printing ink according to claim 13 or 14, which is used for any of gravure printing, flexographic printing, screen printing, offset printing, and inkjet printing. The printing ink according to any one of claims 13 to 15, which is used for printing on any of film packaging, paper packaging, building materials, and decorative paper.